Picolinamides as fungicides

ABSTRACT

This disclosure relates to picolinamides of Formula I and their use as fungicides.

CROSS REFERENCE TO RELATED APPLICATION

The present application claims priority to the benefit of U.S.Provisional Patent Application Ser. No. 62/640,424 filed Mar. 8, 2018and U.S. Provisional Patent Application Ser. No. 62/640,434 filed Mar.8, 2018 the disclosure of which is hereby incorporated by reference inits entirety.

BACKGROUND & SUMMARY

Fungicides are compounds, of natural or synthetic origin, which act toprotect and/or cure plants against damage caused by agriculturallyrelevant fungi. Generally, no single fungicide is useful in allsituations. Consequently, research is ongoing to produce fungicides thatmay have better performance, are easier to use, and cost less.

The present disclosure relates to picolinamides and their use asfungicides. The compounds of the present disclosure may offer protectionagainst ascomycetes, basidiomycetes, deuteromycetes and oomycetes.

One embodiment of the present disclosure may include compounds ofFormula I:

wherein:

Q is

X is hydrogen or C(O)R₄;

Y is hydrogen or C(O)R₄;

Z is N or N⁺→O⁻ and W is O or S;

R₁ is hydrogen or alkyl, substituted with 0, 1 or multiple R₇;

R₂ is methyl;

R₃ is chosen from alkyl, aryl or heteroaryl, each optionally substitutedwith 0, 1 or multiple R₇;

R₄ is chosen from alkoxy or benzyloxy, each optionally substituted with0, 1, or multiple R₇;

R₅ is chosen from hydrogen, alkoxy, or halo, each optionally substitutedwith 0, 1, or multiple R₇;

R₆ is chosen from hydrogen, —C(O)R₈, or —CH₂OC(O)R₈;

R₇ is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkynyl,alkoxy, cyano, or heterocyclyl, each optionally substituted with 0, 1,or multiple R₉;

R₈ is chosen from alkyl, alkoxy, or aryl, each optionally substitutedwith 0, 1, or multiple R₇;

R₉ is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, orheterocyclyl; and

R₁₀ is chosen from hydrogen or alkyl, each substituted with 0, 1 ormultiple R₇.

Another embodiment of the present disclosure may include a fungicidalcomposition for the control or prevention of fungal attack comprisingthe compounds described above and a phytologically acceptable carriermaterial.

Yet another embodiment of the present disclosure may include a methodfor the control or prevention of fungal attack on a plant, the methodincluding the steps of applying a fungicidally effective amount of oneor more of the compounds described above to at least one of the fungus,the plant, and an area adjacent to the plant.

It will be understood by those skilled in the art that the followingterms may include generic “R”-groups within their definitions, e.g.,“the term alkoxy refers to an —OR substituent”. It is also understoodthat within the definitions for the following terms, these “R” groupsare included for illustration purposes and should not be construed aslimiting or being limited by substitutions about Formula I.

The term “alkyl” refers to a branched, unbranched, or saturated cycliccarbon chain, including, but not limited to, methyl, ethyl, propyl,butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, and the like.

The term “alkenyl” refers to a branched, unbranched or cyclic carbonchain containing one or more double bonds including, but not limited to,ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclobutenyl,cyclopentenyl, cyclohexenyl, and the like.

The terms “aryl” and “Ar” refer to any aromatic ring, mono- orbi-cyclic, containing 0 heteroatoms.

The term “heterocyclyl” refers to any aromatic or non-aromatic ring,mono- or bi-cyclic, containing one or more heteroatoms

The term “alkoxy” refers to an —OR substituent.

The term “acyloxy” refers to an —OC(O)R substituent.

The term “cyano” refers to a —C≡N substituent.

The term “hydroxyl” refers to a —OH substituent.

The term “amino” refers to an —N(R)₂ substituent.

The term “arylalkoxy” refers to —O(CH₂)_(n)Ar where n is an integerselected from the list 1, 2, 3, 4, 5, or 6.

The term “haloalkoxy” refers to an —OR—X substituent, wherein X is Cl,F, Br, or I, or any combination thereof.

The term “haloalkyl” refers to an alkyl, which is substituted with Cl,F, I, or Br or any combination thereof.

The term “halogen” or “halo” refers to one or more halogen atoms,defined as F, Cl, Br, and I.

The term “nitro” refers to a —NO₂ substituent.

The term thioalkyl refers to a —SR substituent.

Throughout the disclosure, reference to the compounds of Formula I isread as also including all stereoisomers, for example diastereomers,enantiomers, and mixtures thereof. In another embodiment, Formula (I) isread as also including salts or hydrates thereof. Exemplary saltsinclude, but are not limited to: hydrochloride, hydrobromide,hydroiodide, trifluoroacetate, and trifluoromethane sulfonate.

It is also understood by those skilled in the art that additionalsubstitution is allowable, unless otherwise noted, as long as the rulesof chemical bonding and strain energy are satisfied and the productstill exhibits fungicidal activity.

Another embodiment of the present disclosure is a use of a compound ofFormula I, for protection of a plant against attack by a phytopathogenicorganism or the treatment of a plant infested by a phytopathogenicorganism, comprising the application of a compound of Formula I, or acomposition comprising the compound to soil, a plant, a part of a plant,foliage, and/or roots.

Additionally, another embodiment of the present disclosure is acomposition useful for protecting a plant against attack by aphytopathogenic organism and/or treatment of a plant infested by aphytopathogenic organism comprising a compound of Formula I and aphytologically acceptable carrier material.

DETAILED DESCRIPTION

The compounds of the present disclosure may be applied by any of avariety of known techniques, either as the compounds or as formulationscomprising the compounds. For example, the compounds may be applied tothe roots or foliage of plants for the control of various fungi, withoutdamaging the commercial value of the plants. The materials may beapplied in the form of any of the generally used formulation types, forexample, as solutions, dusts, wettable powders, flowable concentrate, oremulsifiable concentrates.

Preferably, the compounds of the present disclosure are applied in theform of a formulation, comprising one or more of the compounds ofFormula I with a phytologically acceptable carrier. Concentratedformulations may be dispersed in water, or other liquids, forapplication, or formulations may be dust-like or granular, which maythen be applied without further treatment. The formulations can beprepared according to procedures that are conventional in theagricultural chemical art.

The present disclosure contemplates all vehicles by which one or more ofthe compounds may be formulated for delivery and used as a fungicide.Typically, formulations are applied as aqueous suspensions or emulsions.Such suspensions or emulsions may be produced from water-soluble,water-suspendible, or emulsifiable formulations which are solids,usually known as wettable powders; or liquids, usually known asemulsifiable concentrates, aqueous suspensions, or suspensionconcentrates. As will be readily appreciated, any material to whichthese compounds may be added may be used, provided it yields the desiredutility without significant interference with the activity of thesecompounds as antifungal agents.

Wettable powders, which may be compacted to form water-dispersiblegranules, comprise an intimate mixture of one or more of the compoundsof Formula I, an inert carrier and surfactants. The concentration of thecompound in the wettable powder may be from about 10 percent to about 90percent by weight based on the total weight of the wettable powder, morepreferably about 25 weight percent to about 75 weight percent. In thepreparation of wettable powder formulations, the compounds may becompounded with any finely divided solid, such as prophyllite, talc,chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein,gluten, montmorillonite clays, diatomaceous earths, purified silicatesor the like. In such operations, the finely divided carrier andsurfactants are typically blended with the compound(s) and milled.

Emulsifiable concentrates of the compounds of Formula I may comprise aconvenient concentration, such as from about 1 weight percent to about50 weight percent of the compound, in a suitable liquid, based on thetotal weight of the concentrate. The compounds may be dissolved in aninert carrier, which is either a water-miscible solvent or a mixture ofwater-immiscible organic solvents, and emulsifiers. The concentrates maybe diluted with water and oil to form spray mixtures in the form ofoil-in-water emulsions. Useful organic solvents include aromatics,especially the high-boiling naphthalenic and olefinic portions ofpetroleum such as heavy aromatic naphtha. Other organic solvents mayalso be used, for example, terpenic solvents, including rosinderivatives, aliphatic ketones, such as cyclohexanone, and complexalcohols, such as 2-ethoxyethanol.

Emulsifiers which may be advantageously employed herein may be readilydetermined by those skilled in the art and include various nonionic,anionic, cationic and amphoteric emulsifiers, or a blend of two or moreemulsifiers. Examples of nonionic emulsifiers useful in preparing theemulsifiable concentrates include the polyalkylene glycol ethers andcondensation products of alkyl and aryl phenols, aliphatic alcohols,aliphatic amines or fatty acids with ethylene oxide, propylene oxidessuch as the ethoxylated alkyl phenols and carboxylic esters solubilizedwith the polyol or polyoxyalkylene. Cationic emulsifiers includequaternary ammonium compounds and fatty amine salts. Anionic emulsifiersinclude the oilsoluble salts (e.g., calcium) of alkylaryl sulphonicacids, oil-soluble salts or sulfated polyglycol ethers and appropriatesalts of phosphated-polyglycol ether.

Representative organic liquids which may be employed in preparing theemulsifiable concentrates of the compounds of the present disclosure arethe aromatic liquids such as xylene, propyl benzene fractions; or mixednaphthalene fractions, mineral oils, substituted aromatic organicliquids such as dioctyl phthalate; kerosene; dialkyl amides of variousfatty acids, particularly the dimethyl amides of fatty glycols andglycol derivatives such as the n-butyl ether, ethyl ether or methylether of diethylene glycol, the methyl ether of triethylene glycol,petroleum fractions or hydrocarbons such as mineral oil, aromaticsolvents, paraffinic oils, and the like; vegetable oils such as soy beanoil, rape seed oil, olive oil, castor oil, sunflower seed oil, coconutoil, corn oil, cotton seed oil, linseed oil, palm oil, peanut oil,safflower oil, sesame oil, tung oil and the like; esters of the abovevegetable oils; and the like. Mixtures of two or more organic liquidsmay also be employed in the preparation of the emulsifiable concentrate.Organic liquids include xylene, and propyl benzene fractions, withxylene being most preferred in some cases. Surface-active dispersingagents are typically employed in liquid formulations and in an amount offrom 0.1 to 20 percent by weight based on the combined weight of thedispersing agent with one or more of the compounds. The formulations canalso contain other compatible additives, for example, plant growthregulators and other biologically active compounds used in agriculture.

Aqueous suspensions comprise suspensions of one or more water-insolublecompounds of Formula I, dispersed in an aqueous vehicle at aconcentration in the range from about 1 to about 50 weight percent,based on the total weight of the aqueous suspension. Suspensions areprepared by finely grinding one or more of the compounds, and vigorouslymixing the ground material into a vehicle comprised of water andsurfactants chosen from the same types discussed above. Othercomponents, such as inorganic salts and synthetic or natural gums, mayalso be added to increase the density and viscosity of the aqueousvehicle.

The compounds of Formula I can also be applied as granular formulations,which are particularly useful for applications to the soil. Granularformulations generally contain from about 0.5 to about 10 weightpercent, based on the total weight of the granular formulation of thecompound(s), dispersed in an inert carrier which consists entirely or inlarge part of coarsely divided inert material such as attapulgite,bentonite, diatomite, clay or a similar inexpensive substance. Suchformulations are usually prepared by dissolving the compounds in asuitable solvent and applying it to a granular carrier which has beenpreformed to the appropriate particle size, in the range of from about0.5 to about 3 mm. A suitable solvent is a solvent in which the compoundis substantially or completely soluble. Such formulations may also beprepared by making a dough or paste of the carrier and the compound andsolvent, and crushing and drying to obtain the desired granularparticle.

Dusts containing the compounds of Formula I may be prepared byintimately mixing one or more of the compounds in powdered form with asuitable dusty agricultural carrier, such as, for example, kaolin clay,ground volcanic rock, and the like. Dusts can suitably contain fromabout 1 to about 10 weight percent of the compounds, based on the totalweight of the dust.

The formulations may additionally contain adjuvant surfactants toenhance deposition, wetting, and penetration of the compounds onto thetarget crop and organism. These adjuvant surfactants may optionally beemployed as a component of the formulation or as a tank mix. The amountof adjuvant surfactant will typically vary from 0.01 to 1.0 percent byvolume, based on a spray-volume of water, preferably 0.05 to 0.5 volumepercent. Suitable adjuvant surfactants include, but are not limited toethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols,salts of the esters or sulphosuccinic acids, ethoxylatedorganosilicones, ethoxylated fatty amines, blends of surfactants withmineral or vegetable oils, crop oil concentrate (mineral oil(85%)+emulsifiers (15%)); nonylphenol ethoxylate;benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleumhydrocarbon, alkyl esters, organic acid, and anionic surfactant; C₉-C₁₁alkylpolyglycoside; phosphated alcohol ethoxylate; natural primaryalcohol (C₁₂-C₁₆) ethoxylate; di-sec-butylphenol EO-PO block copolymer;polysiloxane-methyl cap; nonylphenol ethoxylate+urea ammonium nitrate;emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate(8EO); tallow amine ethoxylate (15 EO); PEG(400) dioleate-99. Theformulations may also include oil-in-water emulsions such as thosedisclosed in U.S. patent application Ser. No. 11/495,228, the disclosureof which is expressly incorporated by reference herein.

The formulations may optionally include combinations that contain otherpesticidal compounds. Such additional pesticidal compounds may befungicides, insecticides, herbicides, nematocides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the compounds of the present disclosure in the mediumselected for application, and not antagonistic to the activity of thepresent compounds. Accordingly, in such embodiments, the otherpesticidal compound is employed as a supplemental toxicant for the sameor for a different pesticidal use. The compounds of Formula I and thepesticidal compound in the combination can generally be present in aweight ratio of from 1:100 to 100:1.

The compounds of the present disclosure may also be combined with otherfungicides to form fungicidal mixtures and synergistic mixtures thereof.The fungicidal compounds of the present disclosure are often applied inconjunction with one or more other fungicides to control a wider varietyof undesirable diseases. When used in conjunction with otherfungicide(s), the presently claimed compounds may be formulated with theother fungicide(s), tank-mixed with the other fungicide(s) or appliedsequentially with the other fungicide(s). Such other fungicides mayinclude 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol,8-hydroxyquinoline sulfate, ametoctradin, aminopyrifen, amisulbrom,antimycin, Ampelomyces quisqualis, azaconazole, Bacillus subtilis,Bacillus subtilis strain QST713, benalaxyl, benomyl,benthiavalicarb-isopropyl, benzovindiflupyr,benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl,bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeauxmixture, boscalid, bromuconazole, bupirimate, calcium polysulfide,captafol, captan, carbendazim, carboxin, carpropamid, carvone,chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyriumminitans, copper hydroxide, copper octanoate, copper oxychloride, coppersulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid,cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb,diammonium ethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen,diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole,difenzoquat ion, diflumetorim, dimethomorph, dimoxystrobin,diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine,dithianon, dodemorph, dodemorph acetate, dodine, dodine free base,edifenphos, enestrobin, enestroburin, epoxiconazole, ethaboxam,ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol,fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil,fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate,fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluindapyr,flumorph, fluopicolide, fluopyram, fluoroimide, fluoxapiprolin,fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil,flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl,fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine,guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazol,imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadinetriacetate, iminoctadine tris(albesilate), inpyrfluxam, iodocarb,ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb,isofetamide, isoflucypram, isoprothiolane, isopyrazam, isotianil,kasugamycin, kasugamycin hydrochloride hydrate, kresoxium-methyl,laminarin, mancopper, mancozeb, mandipropamid, maneb, mefenoxam,mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuricoxide, mercurous chloride, metalaxyl, metalaxyl-M, metam,metam-ammonium, metam-potassium, metam-sodium, metconazole,methasulfocarb, methyl iodide, methyl isothiocyanate, metiram,metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam,nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fattyacids), orysastrobin, oxadixyl, oxathiapiprolin, oxine-copper,oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole,pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate,penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide,picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate,potassium hydroxyquinoline sulfate, probenazole, prochloraz,procymidone, propamocarb, propamocarb hydrochloride, propiconazole,propineb, proquinazid, prothioconazole, pydiflumetofen, pyrametostrobin,pyraoxystrobin, pyraclostrobin, pyraziflumid, pyrazophos, pyribencarb,pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon,quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract,sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodiumbicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048,tar oils, tebuconazole, tebufloquin, tecnazene, tetraconazole,thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil,tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide,tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine,triticonazole, validamycin, valifenalate, valiphenal, vinclozolin,zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum,Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis,Trichoderma spp.,(RS)-N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide,1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate,1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane,2-(2-heptadecyl-2-imidazolin-1-yl)ethanol,2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide,2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride,2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine,4-(2-nitroprop-1-enyl)phenyl thiocyanateme, ampropylfos, anilazine,azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox,bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl,bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmiumcalcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone,chloraniformethan, chlorfenazole, chlorquinox, climbazole, copperbis(3-phenylsalicylate), copper zinc chromate, coumoxystrobin, cufraneb,cupric hydrazinium sulfate, cuprobam, cyclafuramid, cypendazole,cyprofuram, decafentin, dichlobentiazox, dichlone, dichlozoline,diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon,dipymetitrone, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP,enoxastrobin, ESBP, etaconazole, etem, ethirim, fenaminstrobin,fenaminosulf, fenapanil, fenitropan, fenpicoxamid, florylpicoxamid,flufenoxystrobin, fluopimomide, fluotrimazole, furcarbanil, furconazole,furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin,halacrinate, Hercules 3944, hexylthiofos, ICIA0858, ipfentrifluconazole,ipflufenoquin, isopamphos, isovaledione, mandestrobin, mebenil,mecarbinzid, mefentrifluconazole, metazoxolon, methfuroxam,methylmercury dicyandiamide, metsulfovax, metyltetraprole, milneb,mucochloric anhydride, myclozolin, N-3,5-dichlorophenyl-succinimide,N-3-nitrophenylitaconimide, natamycin,N-ethylmercurio-4-toluenesulfonanilide, nickelbis(dimethyldithiocarbamate), OCH, phenylmercurydimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb;prothiocarb hydrochloride, pyracarbolid, pyrapropoyne, pyridachlometyl,pyridinitril, pyrisoxazole, pyroxychlor, pyroxyfur, quinacetol;quinacetol sulfate, quinazamid, quinconazole, quinofumelin, rabenzazole,salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen,thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos,triarimol, triazbutil, trichlamide, triclopyricarb, triflumezopyrim,urbacid, zarilamid, and any combinations thereof.

Additionally, the compounds described herein may be combined with otherpesticides, including insecticides, nematocides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the compounds of the present disclosure in the mediumselected for application, and not antagonistic to the activity of thepresent compounds to form pesticidal mixtures and synergistic mixturesthereof. The fungicidal compounds of the present disclosure may beapplied in conjunction with one or more other pesticides to control awider variety of undesirable pests. When used in conjunction with otherpesticides, the presently claimed compounds may be formulated with theother pesticide(s), tank-mixed with the other pesticide(s) or appliedsequentially with the other pesticide(s). Typical insecticides include,but are not limited to: 1,2-dichloropropane, abamectin, acephate,acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile,acynonapyr, afidopyropen, alanycarb, aldicarb, aldoxycarb, aldrin,allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone,alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate,amitraz, anabasine, athidathion, azadirachtin, azamethiphos,azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate,barthrin, bendiocarb, benfuracarb, bensultap, benzpyrimoxan,beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin,bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid,broflanilide, bromfenvinfos, bromocyclen, bromo-DDT, bromophos,bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos,butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate,calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran,carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan,cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen,chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride,chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron,chlormephos, chloroform, chloropicrin, chloroprallethrin, chlorphoxim,chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos,chromafenozide, cinerin I, cinerin II, cinerins, cismethrin,cloethocarb, closantel, clothianidin, copper acetoarsenite, copperarsenate, copper naphthenate, copper oleate, coumaphos, coumithoate,crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos,cyanthoate, cyantraniliprole, cyclaniliprole, cyclethrin, cycloprothrin,cyfluthrin, cyhalodiamide, cyhalothrin, cypermethrin, cyphenothrin,cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion,demephion-O, demephion-S, demeton, demeton-methyl, demeton-O,demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon,diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon,dichlofenthion, dichlorvos, dicloromezotiaz, dicresyl, dicrotophos,dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox,dimetan, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex,dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan,dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos,d-limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium,doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC,empenthrin, endosulfan, endothion, endrin, EPN, epofenonane,eprinomectin, epsilon-metofluthrin, epsilon-momfluorothrin,esdepalléthrine, esfenvalerate, etaphos, ethiofencarb, ethion,ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD,ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox,etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos,fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim,fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion,fenthion-ethyl, fenvalerate, fipronil, flometoquin, flonicamid,fluazaindolizine, flubendiamide, flucofuron, flucycloxuron,flucythrinate, fluensulfone, flufenerim, flufenoxuron, flufenprox,flufiprole, fluhexafon, flupyradifurone, flupyrimin, fluvalinate,fluxametamide, fonofos, formetanate, formetanate hydrochloride,formothion, formparanate, formparanate hydrochloride, fosmethilan,fospirate, fosthietan, furathiocarb, furethrin, gamma-cyhalothrin,gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor,heptafluthrin, heptenophos, heterophos, hexaflumuron, HHDN,hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid,imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan,isocarbophos, isocycloseram, isodrin, isofenphos, isofenphos-methyl,isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolinI, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II,juvenile hormone III, kappa-bifenthrin, kappa-tefluthrin, kelevan,kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos,lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben,mazidox, mecarbam, mecarphon, menazon, meperfluthrin, mephosfolan,mercurous chloride, mesulfenfos, metaflumizone, methacrifos,methamidophos, methidathion, methiocarb, methocrotophos, methomyl,methoprene, methoxychlor, methoxyfenozide, methyl bromide, methylisothiocyanate, methylchloroform, methylene chloride, metofluthrin,metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin,milbemycin oxime, mipafox, mirex, molosultap, momfluorothrin,monocrotophos, monomehypo, monosultap, morphothion, moxidectin,naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram,nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl,oxazosulfyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton,para-dichlorobenzene, parathion, parathion-methyl, penfluron,pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate,phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon,phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb,pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassiumthiocyanate, pp′-DDT, prallethrin, precocene I, precocssene II,precocene III, primidophos, profenofos, profluralin, promacyl,promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos,prothoate, protrifenbute, pyflubumide, pyraclofos, pyrafluprole,pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins,pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen,pyriminostrobin, pyrimitate, pyriprole, pyriproxyfen, quassia,quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin,rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, silicagel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodiumthiocyanate, sophamide, spinetoram, spinosad, spiromesifen, spiropidion,spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep,sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb,TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron,tefluthrin, temephos, TEPP, terallethrin, terbufos,tetrachlorantraniliprole, tetrachloroethane, tetrachlorvinphos,tetramethrin, tetramethylfluthrin, tetraniliprole, theta-cypermethrin,thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam,thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap,thiosultap-disodium, thiosultap-monosodium, thuringiensin, tioxazafen,tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene,triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat,trifenofos, triflumezopyrim, triflumuron, trimethacarb, triprene,tyclopyrazoflor, vamidothion, vaniliprole, XMC, xylylcarb,zeta-cypermethrin, zolaprofos, and any combinations thereof.

Additionally, the compounds described herein may be combined withherbicides that are compatible with the compounds of the presentdisclosure in the medium selected for application, and not antagonisticto the activity of the present compounds to form pesticidal mixtures andsynergistic mixtures thereof. The fungicidal compounds of the presentdisclosure may be applied in conjunction with one or more herbicides tocontrol a wide variety of undesirable plants. When used in conjunctionwith herbicides, the presently claimed compounds may be formulated withthe herbicide(s), tank-mixed with the herbicide(s) or appliedsequentially with the herbicide(s). Typical herbicides include, but arenot limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB;2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor,acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim,allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone,amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl,amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton,atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC,beflubutamid, beflubutamid-M, benazolin, bencarbazone, benfluralin,benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendizone,benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop,benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac, bixlozone,borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil,brompyrazon, butachlor, butafenacil, butamifos, butenachlor,buthidazole, buthiuron, butralin, butroxydim, buturon, butylate,cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide,cambendichlor, carbasulam, carbetamide, carboxazole chlorprocarb,carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl,chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon,chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon,chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron,chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid,cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clacyfos,clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop,cloprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate,CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine,cycloate, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cycloxydim,cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid,daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn,di-allate, dicamba, dichlobenil, dichloralurea, dichlormate,dichlorprop, dichlorprop-P, diclofop, diclosulam, diethamquat,diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican,diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn,dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine,dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid,dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP,eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin,ethametsulfuron, ethidimuron, ethiolate, ethofumesate, ethoxyfen,ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam,fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenquinotrione,fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate,flamprop, flamprop-M, flazasulfuron, florasulam, florpyrauxifen,fluazifop, fluazifop-P, fluazolate, flucarbazone, flucetosulfuron,fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin,flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen,fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam,flupropacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone,fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine,furyloxyfen, glufosinate, glufosinate-P, glyphosate, halauxifen,halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P,hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox,imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan,indaziflam, iodobonil, iodomethane, iodosulfuron, iofensulfuron,ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil,isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon,isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop,karbutilate, ketospiradox, lancotrione, lactofen, lenacil, linuron, MAA,MAMA, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb,mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam,metamifop, metamitron, metazachlor, metazosulfuron, metflurazon,methabenzthiazuron, methalpropalin, methazole, methiobencarb,methiozolin, methiuron, methometon, methoprotryne, methyl bromide,methyl isothiocyanate, methyldymron, metobenzuron, metobromuron,metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate,monalide, monisouron, monochloroacetic acid, monolinuron, monuron,morfamquat, MSMA, naproanilide, napropamide, napropamide-M, naptalam,neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen,norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene,orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon,oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat,pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol,pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham,phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate,picloram, picolinafen, pinoxaden, piperophos, potassium arsenite,potassium azide, potassium cyanate, pretilachlor, primisulfuron,procyazine, prodiamine, profluazol, profluralin, profoxydim,proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop,propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron,propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor,pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate,pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor,pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac,pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine,quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron,saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim,siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodiumazide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone,sulfometuron, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA,tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim,terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn,tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin,thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb,tiafenacil, tiocarbazil, tioclorim, tolpyralate, topramezone,tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam,tribenuron, tricamba, triclopyr, tridiphane, trietazine,trifloxysulfuron, trifludimoxazin, trifluralin, triflusulfuron, trifop,trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac,tritosulfuron, vernolate, and xylachlor.

Another embodiment of the present disclosure is a method for the controlor prevention of fungal attack. This method comprises applying to thesoil, plant, roots, foliage, or locus of the fungus, or to a locus inwhich the infestation is to be prevented (for example applying to cerealor grape plants), a fungicidally effective amount of one or more of thecompounds of Formula I. The compounds are suitable for treatment ofvarious plants at fungicidal levels, while exhibiting low phytotoxicity.The compounds may be useful both in a protectant and/or an eradicantfashion.

The compounds have been found to have significant fungicidal effectparticularly for agricultural use. Many of the compounds areparticularly effective for use with agricultural crops and horticulturalplants.

It will be understood by those skilled in the art that the efficacy ofthe compound for the foregoing fungi establishes the general utility ofthe compounds as fungicides.

The compounds have broad ranges of activity against fungal pathogens.Exemplary pathogens may include, but are not limited to, causing agentof wheat leaf blotch (Zymoseptoria tritici), wheat brown rust (Pucciniatriticina), wheat stripe rust (Puccinia striiformis), scab of apple(Venturia inaequalis), powdery mildew of grapevine (Uncinula necator),barley scald (Rhynchosporium secalis), blast of rice (Magnaporthegrisea), rust of soybean (Phakopsora pachyrhizi), glume blotch of wheat(Parastagonospora nodorum), powdery mildew of wheat (Blumeria graminisf. sp. tritici), powdery mildew of barley (Blumeria graminis f. sp.hordei), powdery mildew of cucurbits (Erysiphe cichoracearum),anthracnose of cucurbits (Glomerella lagenarium), leaf spot of beet(Cercospora beticola), early blight of tomato (Alternaria solani), andspot blotch of barley (Cochliobolus sativus). The exact amount of theactive material to be applied is dependent not only on the specificactive material being applied, but also on the particular actiondesired, the fungal species to be controlled, and the stage of growththereof, as well as the part of the plant or other product to becontacted with the compound. Thus, all the compounds, and formulationscontaining the same, may not be equally effective at similarconcentrations or against the same fungal species.

The compounds are effective in use with plants in a disease-inhibitingand phytologically acceptable amount. The term “disease-inhibiting andphytologically acceptable amount” refers to an amount of a compound thatkills or inhibits the plant disease for which control is desired, but isnot significantly toxic to the plant. This amount will generally be fromabout 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm beingpreferred. The exact concentration of compound required varies with thefungal disease to be controlled, the type of formulation employed, themethod of application, the particular plant species, climate conditions,and the like. A suitable application rate is typically in the range fromabout 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per squaremeter, g/m²).

Any range or desired value given herein may be extended or alteredwithout losing the effects sought, as is apparent to the skilled personfor an understanding of the teachings herein.

The compounds of Formula I may be made using well-known chemicalprocedures. Intermediates not specifically mentioned in this disclosureare either commercially available, may be made by routes disclosed inthe chemical literature, or may be readily synthesized from commercialstarting materials utilizing standard procedures.

General Schemes

The following schemes illustrate approaches to generating picolinamidecompounds of Formula (I). The following descriptions and examples areprovided for illustrative purposes and should not be construed aslimiting in terms of substituents or substitution patterns.

Racemic mixtures of Formulas 1.2-Rac, 1.3-Rac and 1.5-Rac, 1.6-Rac,wherein R₃ is as previously defined, can be prepared by the method shownin Scheme 1, step a. Submission of racemic epoxide mixtures of Formulas1.0-Rac and 1.4-Rac, to reaction with an organometallic nucleophile,such

as an aryl magnesium halide, in the presence of a metal halide, such ascopper iodide, in a polar, aprotic solvent, such as tetrahydrofuran(THF) or diethyl ether (Et₂O), at a temperature of about −78° C. to 55°C., affords racemic mixtures of Formulas 1.2-Rac, 1.3-Rac and 1.5-Rac,1.6-Rac, wherein R₃ is as previously defined, and shown in step a.

Racemic mixtures of Formulas 1.2-Rac, 1.3-Rac and 1.5-Rac, 1.6-Rac,wherein R₃ is as previously defined, can be separated into theirindividual enantiomers utilizing a lipase-catalyzed kinetic resolutiondescribed by Akita (Tetrahedron: Asymmetry 2009, 20, 1286-1294) andoutlined in Scheme 2, steps a and b. Subjection of racemic mixtures ofFormulas 1.2-Rac, 1.3-Rac and 1.5-Rac, 1.6-Rac, wherein R₃ is aspreviously defined, to Candida antarctica lipase B (CAL-B) in an

acetylating solvent, such as vinyl acetate, at a temperature of about25° C. to about 60° C., affords the unreacted secondary alcohols ofFormulas 1.2-Abs and 1.5-Abs, wherein R₃ is as originally defined, andthe acetylated compounds of Formulas 2.1-Abs and 2.3-Abs, wherein R₃ isas originally defined. The mixtures can be purified via silica gelchromatography using a hexane-ethyl acetate mixture as the mobile phasegiving the resolved secondary alcohols and acetates of Formulas 1.2-Abs,1.5-Abs, 2.1-Abs and 2.3-Abs, wherein R₃ is as originally defined, andin high enantiomeric excess. The lipase recognition of the secondaryalcohol of 1.2-Rac, 1.3-Rac, 1.5-Rac and 1.6-Rac, wherein R₃ is asoriginally defined, was similar to the empirical rule for the kineticresolution of secondary alcohols (Bornscheuer and Kazlauskus, Hydrolasesin Organic Synthesis; Wiley-VCH, 2006). Treatment of acetates ofFormulas 2.1-Abs and 2.3-Abs, wherein R₃ is as originally defined, witha carbonate base, such as potassium carbonate, in an alcoholic solvent,such as methanol, at a temperature of about 25° C. to about 60° C.,affords the resolved secondary alcohols of Formulas 2.2-Abs and 2.4-Abs,wherein R₃ is as originally defined.

Compounds of Formula 3.2, wherein R₁, R₂, R₃, and R₁₀, are as originallydefined, may be prepared according to the method outlined in Scheme 3,step a. Alcohols of Formula 3.0, wherein R₂ and R₃, are as originallydefined, can be treated with compounds of Formula 3.1, wherein R₁ andR₁₀ are as originally defined, a coupling reagent, such as3-(ethyliminomethyleneamino)-N,N-dimethylpropan-1-amine hydrochloride(EDC) or a polymer-supported carbodiimide (PS-CDT), and a catalyst, suchas N,N-dimethylpyridin-4-amine (DMAP), in a halogenated or polar,aprotic solvent, such as (CH₂Cl₂) or THF to afford compounds of Formula3.2, wherein R₁, R₂, R₃, and R₁₀, are as originally defined, as shown instep a.

Compounds of Formula 4.5, wherein R₁, R₂, R₃, R₅, and R₁₀, are asoriginally defined, can be prepared according to the methods outlined inScheme 4, steps a-d. Compounds of Formula 3.2, wherein R₁, R₂, R₃, andR₁₀, are as originally defined, can be treated with an acid, such as a 4Normal (N) solution of hydrogen chloride (HCl) in dioxane, in ahalogenated solvent such as CH₂Cl₂ to afford compounds of Formula 4.1,wherein R₁, R₂, R₃, and R₁₀, as shown in step a. Compounds of Formula4.2, wherein R₁, R₂, R₃, and R₁₀, are as originally defined, can beprepared by treating compounds of Formula 3.2, wherein R₁, R₂, R₃, andR₁₀, are as originally defined, with an acid, such as2,2,2-trifluoroacetic acid, in a halogenated solvent such as CH₂Cl₂, asshown in step c. Compounds of Formulas 4.1 and 4.2, wherein R₁, R₂, R₃,and R₁₀, are as originally defined, can be treated with compounds ofFormula 4.3, wherein R₅ is as originally defined, in the presence of abase, such as diisopropylethylamine, and a peptide coupling reagent,such as benzotriazol-1-yl-oxytripyrrolidinophosphoniumhexafluorophosphate (PyBOP) orO-(7-azabenzo-triazol-1-yl)-N,N,N′,N′tetramethyluroniumhexafluorophosphate (HATU), in a halogenated solvent such as CH₂Cl₂, toafford compounds of Formula 4.5, wherein R₁, R₂, R₃, R₅ and R₁₀, are asoriginally defined, as shown in steps b and d.

Compounds of Formula 5.1, wherein R₁, R₂, R₃, R₅ and R₁₀, are asoriginally defined, can be prepared according to the method outlined inScheme 5, steps a orb. Compounds of Formula 4.5, wherein R₁, R₂, R₃, R₅and R₁₀, are as originally defined, can be treated with an appropriatealkyl halide, with or without a reagent such as sodium iodide (NaI) andan alkali carbonate base, such as sodium (Na₂CO₃) or potassium carbonate(K₂CO₃), in a solvent such as acetone, at a temperature of about 25° C.to about 50° C., as shown in step a. Or, alternatively, by treatmentwith an acyl halide or anhydride in the presence of an amine base, suchas pyridine, triethylamine (NEt₃), DMAP, or mixtures thereof, in anaprotic solvent, such as CH₂Cl₂, to afford compounds of Formula 5.1,wherein R₁, R₂, R₃, R₅, R₆, and R₁₀, are as originally defined, as shownin step b.

Compounds of Formula 6.1 and 6.2, wherein R₁, R₂, R₃, R₅, R₆, and R₁₀,are as originally defined, can be prepared according to the methodoutlined in Scheme 6, steps a and b. Compounds of Formula 4.5, whereinR₁, R₂, R₃, R₅, and R₁₀, are as originally defined, can be treated witha thionating reagent such as phosphorus pentasulfide, an additive, suchas hexamethyldisiloxane, optionally in a polar aprotic solvent such asacetonitrile (CH₃CN), at a temperature of about 0° C. to 80° C. toafford compounds of Formula 6.1, wherein R₁, R₂, R₃, R₅ and R₁₀, are asoriginally defined, and shown in step a. It will be understood by thoseskilled in the art that compounds such as Formula 6.1 may also beprepared using other thionating agents including, but not limited to:sulfur, sulfhydric acid, sodium sulfide, sodium hydrosulfide, borontrisulfide, bis(diethylaluminum)sulfide, ammonium sulfide, Lawesson'sreagent, ammonium O,O′-diethyl dithiophosphate, rhodanine, or a polymersupported thionating reagent. Additives can include, but not limited to,aluminum oxide (Al₂O₃); inorganic bases, such as potassium carbonate andsodium bicarbonate; organic bases, such as triethylamine,diethylaniline, pyridine and morpholine. Optional solvents can include,but not limited to, aliphatic, alicyclic or aromatic hydrocarbons, suchas hexane, cyclohexane or toluene; halogenated hydrocarbons, such asdichloromethane, 1,2-dichloroethane and chlorobenzene; ethers, such asdiethyl ether, 1,4-dioxane, THF and 1,2-dimethoxyethane; and other polaraprotic solvents such as pyridine and hexamethylphosphoramide (HMPA). Instep b, treatment of compounds of Formula 6.1, wherein R₁, R₂, R₃, R₅and R₁₀, are as originally defined, with an appropriate alkyl halidewith or without a reagent such as sodium iodide (NaI) and an alkalicarbonate base, such as sodium carbonate (Na₂CO₃) or potassium carbonate(K₂CO₃), in a polar aprotic solvent, such as acetone, at a temperatureof about 55° C., or by treatment with an acyl halide or anhydride in thepresence of an amine base, such as pyridine, Et₃N, DMAP, or mixturesthereof, in an optional aprotic solvent such as CH₂Cl₂, at a temperatureof about 23° C., can afford compounds of Formula 6.2 wherein R₁, R₂, R₃,R₅, R₆, and R₁₀, are as originally defined.

Compounds of Formula 7.1, wherein R₁, R₂, R₃, R₅ and R₁₀, are asoriginally defined, can be prepared according to the method outlined inScheme 7, step a. Compounds of Formula 4.5, wherein R₁, R₂, R₃, R₅ andR₁₀, are as originally defined, can be treated with a oxidizing reagentsuch as m-chloroperbenzoic acid (mCPBA) in a polar solvent such asCH₂Cl₂, at a temperature of about 0° C. to 50° C., to give compounds ofFormula 7.1, wherein R₁, R₂, R₃, R₅ and R₁₀, are as previously defined,and shown in a. It will be understood by those skilled in the art thatcompounds of Formula 7.1, wherein R₁, R₂, R₃, R₅ and R₁₀, are asoriginally defined, may also be prepared using other oxidizing agents,including, but not limited to: hydrogen peroxide, hydrogen

peroxide-urea complex, magnesium monoperoxyphthalate hexahydrate (MMPP),peroxyacetic acid, oxone, sodium perchlorate or dimethyl dioxirane.

Compounds of Formula 8.1 wherein R₁, R₂, R₃, R₅ and R₁₀, are asoriginally defined, can be prepared according to the method outlined inScheme 8, step a. Compounds of Formula 4.5, wherein R₁, R₂, R₃, R₅ andR₁₀, are as originally defined, can be treated with a deactivatedcarbonyl reagent such as triphosgene, with a base, such as pyridine, andin a polar solvent, such as CH₂Cl₂, at a temperature of about 0° C. to50° C. to afford compounds of Formula 8.1, wherein R₁, R₂, R₃, R₅ andR₁₀, are as originally defined, as depicted in a.

EXAMPLES Example 1A: Preparation of Racemicthreo-3-(2,4-dimethylphenyl)butan-2-ol

To a suspension of freshly activated magnesium metal shavings (1.14 g,46.80 mmol) in anhydrous Et₂O (20 mL) was added dropwise1-bromo-2,4-dimethylbenzene (8 g, 43.20 mmol). The mixture was gentlyheated at slight reflux (36° C.) for 5 hours (hr). The resulting darkbrown solution was added via syringe to a flask containing copper (I)iodide (4.12 g, 21.61 mmol) suspended in Et₂O (50 mL) at −20° C. Thedark yellow suspension was stirred for 15 minutes (min) at −20° C. andthen cooled to −50° C. Racemic trans-butene epoxide (1.3 g, 18.01 mmol)was slowly added dropwise followed by warming the reaction to roomtemperature and stirring overnight. The mixture was then cooled to 0° C.and slowly quenched by the addition of a saturated aqueous ammoniumchloride (NH₄Cl) solution. The mixture was filtered through a pad ofCelite and the pad was rinsed thoroughly with ethyl acetate. The organicsolution was washed with saturated NH₄Cl solution and brine. Thesolution was dried (magnesium sulfate (MgSO₄)), filtered andconcentrated under reduced pressure. The residue was purified viaautomated flash column chromatography (SiO₂, 0-40% ethyl acetate/hexanesgradient) to give racemic threo-3-(2,4-dimethylphenyl)butan-2-ol as ayellow oil (813 mg, 25%): ¹H NMR (500 MHz, CDCl₃) δ 7.06 (d, J=8.5 Hz,1H), 7.01-6.97 (m, 2H), 3.94-3.82 (m, 1H), 2.97 (p, J=6.9 Hz, 1H), 2.29(d, J=7.7 Hz, 6H), 1.50 (d, J=3.9 Hz, 1H), 1.28 (d, J=7.0 Hz, 3H), 1.11(d, J=6.3 Hz, 3H); ¹³C NMR (126 MHz, CDCl₃) δ 139.99, 135.49, 135.38,131.31, 126.81, 126.18, 71.92, 41.42, 21.25, 20.87, 19.85, 16.06; EIMSm/z 178.

Example 1B: Preparation of Racemic erythro-3-(o-tolyl)butan-2-ol

To a −20° C. suspension of copper(I) iodide (4.15 g, 21.60 mmol) inanhydrous Et₂O (40 mL) was added 2-methylphenylmagnesium bromide (2.0 Min Et₂O, 22.5 mL, 43.20 mmol) slowly dropwise. After stirring for 30min, the orange suspension was cooled to −78° C., and racemic cis-buteneepoxide (1.3 g, 18.01 mmol) was slowly added. The dry ice bath wasremoved and the mixture was allowed to slowly warm to ambienttemperature and stirred overnight. The mixture was cooled with an icebath to 0° C. and quenched slowly by the dropwise addition of asaturated aqueous NH₄Cl solution. The mixture was warmed to roomtemperature and filtered through Celite, followed by rinsing the padwith ethyl acetate (EtOAc). The resulting filtrate was washed withsaturated aqueous NH₄Cl solution and brine. The solution was then dried(MgSO₄) and concentrated under reduced pressure. The residue waspurified automated flash column chromatography (SiO₂, 0-30% ethylacetate/hexanes gradient) to give racemic erythro-3-(o-tolyl)butan-2-ol(2.05 g, 69%) as a yellow oil: ¹H NMR (500 MHz, CDCl₃) δ 7.34-7.01 (m,4H), 3.92 (p, J=6.3 Hz, 1H), 3.01 (p, J=7.1 Hz, 1H), 2.36 (s, 3H), 1.47(s, 1H), 1.28 (d, J=6.1 Hz, 3H), 1.19 (d, J=7.0 Hz, 3H); ¹³C NMR (126MHz, CDCl₃) δ 142.14, 136.84, 130.61, 126.49, 125.81, 72.33, 42.62,20.47, 19.93, 17.88; EIMS m/z 164.

Example 1C: Preparation of Racemic threo-3-phenylbutan-2-ol

To a suspension of copper (I) iodide (1.86 g, 9.76 mmol) in ethyl ether(18.0 mL) was added dropwise phenyllithium (1.9 M in butyl ether, 10.3mL, 19.53 mmol) at 0° C. under a nitrogen atmosphere. After stirring at0° C. for 1 hr, racemic trans-2,3-dimethyloxirane (0.64 g, 8.88 mmol)was added dropwise followed by removal of the ice bath and warming toroom temperature with stirring over 2 hr. The reaction mixture wasquenched with water (20 mL), filtered through a pad of Celite, andextracted with ethyl ether (3×20 mL). The organics were passed through aphase separator and concentrated in vacuo. The crude residue waspurified via automated flash column chromatography (SiO₂, 0-25%acetone/hexanes gradient) to furnish racemic threo-3-phenylbutan-2-ol(1.33 g, 8.85 mmol, 99%) as orange oil: ¹H NMR (400 MHz, CDCl₃) δ7.38-7.12 (m, 5H), 3.91-3.84 (m, 1H), 2.80-2.68 (m, 1H), 1.43 (s, 1H),1.33 (d, J=7.1 Hz, 3H), 1.09 (d, J=6.3 Hz, 3H). The spectral data wasconsistent with those reported in the literature: Tetrahedron 1981, 37,709-713.

Example 2: Preparation of (2S,3S)-3-(2,4-dimethylphenyl)butan-2-ol and(2R,3R)-3-(2,4-dimethylphenyl)butan-2-ol Step 1: Preparation of(2S,3S)-3-(2,4-dimethylphenyl)butan-2-ol and(2R,3R)-3-(2,4-dimethylphenyl)butan-2-yl acetate

A vial containing a solution of the racemictrans-3-(2,4-dimethylphenyl)butan-2-ol (800 mg, 4.49 mmol) dissolved invinyl acetate (15 mL) was charged with beads of Novozym 435 Lipase(CAL-B, 1.6 g, 4.49 mmol). The vial was placed in an orbital shaker andwas shaken at 200 rpm and heated at 55° C. for 7.5 hrs. The reaction wascooled and filtered through a frit disk with an EtOAc rinse. The eluentwas concentrated under reduced pressure to give 906 mg of a crude yellowoil. The residue was purified via flash column chromatography (SiO₂,0-20% ethyl acetate/hexanes gradient) to afford(2R,3R)-3-(2,4-dimethylphenyl)butan-2-yl acetate (clear oil, 466 mg,47%) followed by (2S,3S)-3-(2,4-dimethylphenyl)butan-2-ol (clear yellowoil, 357 mg, 43%). Acetate: ¹H NMR (500 MHz, CDCl₃) δ 7.07 (d, J=7.7 Hz,1H), 7.01-6.97 (m, 2H), 5.08 (dq, J=8.5, 6.3 Hz, 1H), 3.16-3.05 (m, 1H),2.30 (s, 3H), 2.28 (s, 3H), 2.06 (s, 3H), 1.21 (d, J=6.9 Hz, 3H), 1.06(d, J=6.3 Hz, 3H); ¹³C NMR (126 MHz, CDCl₃) δ 170.80, 138.92, 135.56,135.42, 131.22, 126.93, 126.33, 75.09, 39.48, 21.34, 20.89, 19.88,18.34, 17.96; EIMS m/z 220. Alcohol: ¹H NMR (500 MHz, CDCl₃) δ 7.06 (d,J=8.5 Hz, 1H), 7.01-6.97 (m, 2H), 3.88 (tt, J=9.2, 4.7 Hz, 1H), 2.97 (p,J=6.9 Hz, 1H), 2.30 (s, 3H), 2.28 (s, 3H), 1.49 (d, J=3.5 Hz, 1H), 1.28(d, J=7.0 Hz, 3H), 1.11 (d, J=6.3 Hz, 3H); ¹³C NMR (126 MHz, CDCl₃) δ140.00, 135.49, 135.38, 131.31, 126.82, 126.18, 71.92, 41.43, 21.25,20.87, 19.85, 16.07; EIMS m/z 178. The enatiomeric ratio of(2S,3S)-3-(2,4-dimethylphenyl)butan-2-ol was determined to be 96:4 byanalysis via enatiomeric HPLC separation (210 nm wavelength).

Step 2: Preparation of (2R,3R)-3-(2,4-dimethylphenyl)butan-2-ol

To a solution containing (2R,3R)-3-(2,4-dimethylphenyl)butan-2-ylacetate prepared above (458 mg, 2.08 mmol) dissolved in methanol (4.2mL) was added potassium carbonate (431 mg, 3.12 mmol). The mixture wasstirred at ambient temperature for 1.5 hr, then heated to 50° C. for 2hr. The reaction was cooled and concentrated under reduced pressure. Theresidue was diluted with acetone and passed through a small plug ofsilica gel, washing the pad well with acetone. The solvent wasconcentrated in vacuo to give (2R,3R)-3-(2,4-dimethylphenyl)butan-2-ol(332 mg, 90%) as a yellow oil: ¹H NMR (500 MHz, CDCl₃) δ 7.06 (d, J=8.5Hz, 1H), 7.01-6.97 (m, 2H), 3.88 (p, J=6.3 Hz, 1H), 2.97 (p, J=6.9 Hz,1H), 2.30 (s, 3H), 2.28 (s, 3H), 1.49 (s, 1H), 1.28 (d, J=7.0 Hz, 3H),1.11 (d, J=6.3 Hz, 3H); ¹³C NMR (126 MHz, CDCl₃) δ 140.00, 135.49,135.38, 131.31, 126.82, 126.18, 71.92, 41.43, 21.26, 20.87, 19.85,16.07; EIMS m/z 178. The enatiomeric ratio of the alcohol was determinedto be 7:93 via analysis by enatiomeric HPLC.

Example 3: Preparation of (2S,3S)-3-phenylbutan-2-ol(tert-butoxycarbonyl)-L-alaninate

To a solution of (2S,3S)-3-phenylbutan-2-ol (0.23 g, 1.53 mmol)dissolved in methylene chloride (7.7 mL) was addedN-ethyl-N-(3-dimethylaminopropyl)carbodiimide hydrochloride (0.59 g,3.06 mmol) and N,N-dimethylpyridin-4-amine (19 mg, 0.15 mmol). Thereaction mixture was purged with nitrogen, stirred over 16 hr, followedby concentration in vacuo. The crude residue was purified via automatedflash column chromatography (SiO₂, 0-20% ethyl acetate/hexanes gradient)to afford (2S,3S)-3-phenylbutan-2-yl (tert-butoxycarbonyl)-L-alaninate(0.43 g, 1.34 mmol, 83% yield) as colorless oil: ¹H NMR (400 MHz, CDCl₃)δ 7.35-7.25 (m, 2H), 7.27-7.15 (m, 3H), 5.12-5.01 (m, 2H), 4.35-4.26 (m,1H), 2.95-2.83 (m, 1H), 1.45 (s, 9H), 1.37 (d, J=7.2 Hz, 3H), 1.29 (d,J=7.1 Hz, 3H), 1.09 (d, J=6.3 Hz, 3H); ¹³C NMR (126 MHz, CDCl₃) δ 172.9,155.0, 143.0, 128.5, 127.8, 126.7, 79.7, 76.1, 49.5, 45.1, 28.3, 18.9,18.3, 17.5; IR (thin film) 3355, 2978, 2934, 1711, 1495, 1452, 1366,1161, 1087, 1065, 701 cm⁻¹.

Example 4: Preparation of(2S,3S)-3-phenylbutan-2-yl(3-hydroxy-4-methoxypicolinoyl)-L-alaninateStep 1: Preparation of(2S,3S)-3-phenylbutan-2-yl-L-alaninate-hydrochloride

To neat (2S,3S)-3-phenylbutan-2-ol (tert-butoxycarbonyl)-L-alaninate(0.42 g, 1.31 mmol) was added dropwise a solution of HCl dissolved indioxane (4 M, 3.3 mL, 13.07 mmol) under nitrogen. Upon stirring for 16hr, the reaction mixture was concentrated in vacuo to afford crude(2S,3S)-3-phenylbutan-2-yl-L-alaninate-hydrogen chloride as white solid,which was directly carried to the next step: HRMS-ESI (m/z) [M+H]+calc'd for C₁₃H₂₀NO₂, 222.1489; found, 222.1485.

Step 2: Preparation of (2S,3S)-3-phenylbutan-2-yl(3-hydroxy-4-methoxypicolinoyl)-L-alaninate

To a solution of (2S,3S)-3-phenylbutan-2-yl-L-alaninate-hydrogenchloride, 3-hydroxy-4-methoxypicolinic acid (0.24 g, 1.44 mmol), and(benzotriazol-1-yloxy)tripyrrolidinophosphonium hexafluorophosphate(0.75 g, 1.44 mmol) dissolved in methylene chloride (6.5 mL) was addeddropwise N,N-diisopropylethylamine (0.75 mL, 4.31 mmol) under nitrogen.Upon stirring for 16 hr, the reaction mixture was concentrated in vacuo.The crude residue was purified via automated flash column chromatography(SiO₂, 0-45% acetone/hexanes gradient) to afford(2S,3S)-3-phenylbutan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaninate(0.46 g, 1.173 mmol, 90% yield) as colorless oil: ¹H NMR (500 MHz,CDCl₃) δ 12.16 (s, 1H), 8.50 (d, J=8.0 Hz, 1H), 8.01 (d, J=5.2 Hz, 1H),7.32-7.27 (m, 2H), 7.24-7.16 (m, 3H), 6.88 (d, J=5.2 Hz, 1H), 5.11 (dq,J=7.7, 6.3 Hz, 1H), 4.77-4.67 (m, 1H), 3.95 (s, 3H), 2.97-2.87 (m, 1H),1.54 (d, J=7.2 Hz, 3H), 1.31 (d, J=7.0 Hz, 3H), 1.13 (d, J=6.3 Hz, 3H);IR (thin film) 2978, 2937, 1733, 1647, 1527, 1451, 1262, 1147, 701 cm⁻¹;HRMS-ESI (m/z) [M+H]+ calc'd for C₂₀H₂₅N₂O₅, 373.1758; found, 373.1752.

Example 5A: Preparation of(2S,3S)-3-phenylbutan-2-yl(3-acetoxy-4-methoxypicolinoyl)-L-alaninate

To a solution containing (2S,3S)-3-phenylbutan-2-yl(3-hydroxy-4-methoxypicolinoyl)-L-alaninate (84 mg, 0.23 mmol) dissolvedin pyridine (1.0 mL) was added dropwise acetic anhydride (0.25 mL, 2.65mmol) under nitrogen. Upon stirring for 30 min, the reaction mixture wasconcentrated in vacuo, followed by azeotroping with toluene (10 mL). Thecrude residue was purified via automated flash column chromatography(SiO₂, 0-40% acetone/hexanes gradient) to afford(2S,3S)-3-phenylbutan-2-yl(3-acetoxy-4-methoxypicolinoyl)-L-alaninate(90 mg, 0.21 mmol, 91% yield) as colorless oil: ¹H NMR (500 MHz, CDCl₃)δ 8.56 (s, 1H), 8.34 (d, J=5.5 Hz, 1H), 7.32-7.27 (m, 2H), 7.24-7.16 (m,3H), 7.01 (d, J=5.5 Hz, 1H), 5.09 (dq, J=7.7, 6.3 Hz, 1H), 4.77-4.67 (m,1H), 3.91 (s, 3H), 2.96-2.86 (m, 1H), 2.41 (s, 3H), 1.49 (d, J=7.2 Hz,3H), 1.30 (d, J=7.0 Hz, 3H), 1.10 (d, J=6.3 Hz, 3H); IR (thin film)3377, 2980, 2938, 1770, 1732, 1674, 1507, 1310, 1198, 1174, 702 cm⁻¹;HRMS-ESI (m/z) [M+H]+ calc'd for C₂₂H₂₇N₂O₆, 415.1864; found, 415.1859.

Example 5B: Preparation of(2S,3R)-3-(o-tolyl)butan-2-yl(3-(acetoxymethoxy)-4-methoxypicolinoyl)-L-alaninate

To a solution containing (2S,3R)-3-(o-tolyl)butan-2-yl(3-hydroxy-4-methoxypicolinoyl)-L-alaninate dissolved in 0.7 mL ofacetone was added potassium carbonate (39 mg, 0.279 mmol) followed bybromomethyl acetate (27 μL, 0.279 mmol). The solution was heated at 50°C. for 1.5 hr. The reaction mixture was cooled and concentrated invacuo. The crude residue was purified via automated flash columnchromatography (SiO₂, 0-80% acetone/hexanes gradient) to afford(2S,3R)-3-(o-tolyl)butan-2-yl(3-(acetoxymethoxy)-4-methoxypicolinoyl)-L-alaninate(63 mg, 93% yield) as a thick oil: ¹H NMR (500 MHz, CDCl₃) δ 8.26 (d,J=5.4 Hz, 1H), 8.22 (t, J=7.4 Hz, 1H), 7.22-7.03 (m, 4H), 6.93 (d, J=5.4Hz, 1H), 5.73 (dd, J=5.6, 1.8 Hz, 2H), 5.16 (dq, J=8.1, 6.3 Hz, 1H),4.58-4.51 (m, 1H), 3.90 (s, 3H), 3.31-3.22 (m, 1H), 2.37 (s, 3H), 2.06(s, 3H), 1.31 (d, J=6.2 Hz, 3H), 1.24 (d, J=7.0 Hz, 3H), 1.03 (d, J=7.2Hz, 3H); ¹³C NMR (126 MHz, CDCl₃) δ 172.26, 170.26, 162.87, 160.25,145.68, 143.94, 142.57, 141.57, 136.03, 130.21, 126.16, 125.94, 109.49,89.57, 75.57, 56.16, 48.08, 39.48, 20.87, 19.84, 17.92, 17.77, 17.05;HRMS-ESI (m/z) [M+H]⁺ calc'd for C₂₄H₃₀N₂O₇, 459.2126; found, 459.2121.

Example 5C: Preparation of4-methoxy-2-(((S)-1-oxo-1-(((2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2-yl)oxy)propan-2-yl)carbamoyl)pyridin-3-ylisobutyrate

To a solution containing(2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2-yl(3-hydroxy-4-methoxypicolinoyl)-L-alaninate(283.9 mg, 0.645 mmol) and N,N-dimethylpyridin-4-amine (15.75 mg, 0.129mmol) was prepared in CH₂Cl₂ (2 mL). To this solution was addedtriethylamine (0.180 mL, 1.289 mmol) followed by isobutyryl chloride(0.102 mL, 0.967 mmol). The resultant clear reaction was stirred atambient temperature overnight. The reaction was concentrated underreduced pressure to afford an orange oil under a stream of N₂. The cruderesidue was purified via automated flash column chromatography (SiO₂,0-100% ethyl acetate/hexanes gradient) to afford4-methoxy-2-(((S)-1-oxo-1-(((2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2-yl)oxy)propan-2-yl)carbamoyl)pyridin-3-ylisobutyrate (252.3 mg, 0.494 mmol, 77% yield) as a yellow oil: ¹H NMR(400 MHz, CDCl₃) δ 8.50 (d, J=7.4 Hz, 1H), 8.34 (d, J=5.4 Hz, 1H), 7.64(dd, J=8.0, 1.3 Hz, 1H), 7.54-7.47 (m, 1H), 7.44 (d, J=7.8 Hz, 1H), 7.31(t, J=7.5 Hz, 1H), 6.99 (d, J=5.4 Hz, 1H), 5.26-5.11 (m, 1H), 4.76 (p,J=7.3 Hz, 1H), 3.89 (s, 3H), 3.34 (p, J=6.6 Hz, 1H), 2.96 (hept, J=7.0Hz, 1H), 1.54 (d, J=7.2 Hz, 3H), 1.36 (dd, J=7.0, 1.3 Hz, 6H), 1.28 (d,J=6.8 Hz, 3H), 1.10 (d, J=6.3 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ−58.25; IR (thin film) 3383, 2981, 1737, 1679, 1505, 1310, 1114, 1045,732 cm⁻¹; HRMS-ESI (m/z) [M+H]⁺ calc'd for C₂₅H₃₀F₃N₂O₆, 511.2050;found, 511.2048.

Example 6: Preparation of (2S,3S)-3-(2,4-dimethylphenyl)butan-2-yl(3-acetoxy-4-methoxypyridine-2-carbonothioyl)-L-alaninate Step 1:Preparation of(2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2-yl(3-hydroxy-4-methoxypyridine-2-carbonothioyl)-L-alaninate

To a solution containing (2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2-yl(3-hydroxy-4-methoxypicolinoyl)-L-alaninate (120.1 mg, 0.273 mmol)dissolved in acetonitrile (2.73 mL) was added phosphorus pentasulfide(121 mg, 0.545 mmol) followed by 1,1,1,3,3,3-hexamethyldisiloxane (291μL, 1.363 mmol) added in one portion. The reaction was heated to 45° C.for 30 min. The reaction was cooled, diluted with CH₂Cl₂ (10 mL) andquenched by the addition of saturated aqueous NaHCO₃ (10 mL). The layerswere separated and the aqueous layer was extracted with CH₂Cl₂ (3×10mL). The combined organic layers were passed through a phase separatorand concentrated to a yellow oil. The crude material was purified viaautomated flash column chromatography (SiO₂, 0-50% acetone/hexanesgradient) to afford(2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2-yl(3-hydroxy-4-methoxypyridine-2-carbonothioyl)-L-alaninate(104.7 mg, 0.229 mmol, 84% yield) as a yellow semisolid; ¹H NMR (400MHz, CDCl₃) δ 12.93 (s, 1H), 10.74 (d, J=7.6 Hz, 1H), 8.00 (d, J=5.1 Hz,1H), 7.73-7.59 (m, 1H), 7.51 (t, J=7.7 Hz, 1H), 7.43 (d, J=7.8 Hz, 1H),7.33 (t, J=7.5 Hz, 1H), 6.89 (d, J=5.1 Hz, 1H), 5.30-5.18 (m, 1H), 5.14(p, J=7.2 Hz, 1H), 3.96 (s, 3H), 3.37 (p, J=6.8 Hz, 1H), 1.69 (dd,J=7.2, 3.2 Hz, 3H), 1.30 (d, J=6.8 Hz, 3H), 1.14 (d, J=6.3 Hz, 3H); ¹⁹FNMR (376 MHz, CDCl₃) δ −58.23; IR (thin film) 3087, 2984, 1737, 1513,1484, 1311, 1151, 1118, 800, 771 cm⁻¹; HRMS-ESI (m/z) [M+H]⁺ calc'd forC₂₁H₂₄F₃N₂O₄S, 457.1403; found, 457.1399.

Step 2: Preparation of (2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2-yl(3-acetoxy-4-methoxypyridine-2-carbonothioyl)-L-alaninate

To a solution containing(2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2-yl(3-hydroxy-4-methoxypyridine-2-carbonothioyl)-L-alaninate(53.9 mg, 0.118 mmol) and N,N-dimethylpyridin-4-amine (2.89 mg, 0.024mmol) dissolved in CH₂Cl₂ (2 mL) was added triethylamine (0.041 mL,0.295 mmol) followed by acetyl chloride (9.23 μL, 0.130 mmol). Theresultant light orange reaction was stirred at ambient temperature for18 hr. The reaction was concentrated under reduced pressure to afford anorange oil under a stream of N₂. The crude residue was purified viaautomated flash column chromatography (SiO₂, 0-50% acetone/hexanesgradient) to afford(2S,3S)-3-(2-(trifluoromethyl)phenyl)butan-2-yl(3-acetoxy-4-methoxypyridine-2-carbonothioyl)-L-alaninate(51.7 mg, 0.104 mmol, 88% yield) as a yellow oil: ¹H NMR (400 MHz,CDCl₃) δ 9.96 (d, J=7.3 Hz, 1H), 8.34 (d, J=5.5 Hz, 1H), 7.71-7.59 (m,1H), 7.59-7.47 (m, 1H), 7.44 (d, J=7.8 Hz, 1H), 7.39-7.28 (m, 1H), 7.00(d, J=5.5 Hz, 1H), 5.28-5.15 (m, 2H), 3.91 (s, 3H), 3.42-3.29 (m, 1H),2.37 (s, 3H), 1.64 (d, J=7.2 Hz, 3H), 1.30 (d, J=6.8 Hz, 3H), 1.12 (d,J=6.3 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.23; HRMS-ESI (m/z) [M+H]⁺calc'd for C₂₃H₂₆F₃N₂O₅S, 499.1509; found, 499.1508.

Example 7: Preparation of3-hydroxy-4-methoxy-2-(((S)-1-oxo-1-(((2S,3S)-3-phenylbutan-2-yl)oxy)propan-2-yl)carbamoyl)pyridine1-oxide

To a solution containing (2S,3S)-3-phenylbutan-2-yl(3-hydroxy-4-methoxypicolinoyl)-L-alaninate (54 mg, 0.15 mmol) dissolvedin methylene chloride (1.0 mL) was added m-CPBA (50 mg, 0.29 mmol). Uponstirring for 30 min at room temperature, the reaction mixture wasconcentrated in vacuo. The crude residue was purified via automatedflash column chromatography (SiO₂, 0-50% acetone/hexanes gradient) toafford3-hydroxy-4-methoxy-2-(((S)-1-oxo-1-(((2S,3S)-3-phenylbutan-2-yl)oxy)propan-2-yl)carbamoyl)pyridine1-oxide (51 mg, 0.13 mmol, 86% yield) as viscous, pale yellow oil: ¹HNMR (500 MHz, CDCl₃) δ 14.39 (s, 1H), 12.82 (d, J=6.9 Hz, 1H), 7.89 (d,J=7.2 Hz, 1H), 7.32-7.25 (m, 2H), 7.25-7.15 (m, 3H), 6.78 (d, J=7.2 Hz,1H), 5.10 (dq, J=8.1, 6.3 Hz, 1H), 4.75-4.64 (m, 1H), 3.97 (s, 3H),2.96-2.86 (m, 1H), 1.56 (d, J=7.2 Hz, 3H), 1.30 (d, J=6.9 Hz, 3H), 1.12(d, J=6.2 Hz, 3H); IR (thin film) 2978, 2937, 1735, 1643, 1569, 1479,1452, 1211, 1154, 729, 702 cm⁻¹; HRMS-ESI (m/z) [M+H]+ calc'd forC₂₀H₂₅N₂O₆, 389.1707; found, 389.1703.

Example 8: Preparation of (2S,3S)-3-phenylbutan-2-yl(S)-2-(8-methoxy-2,4-dioxo-2H-pyrido[2,3-e][1,3]oxazin-3(4H)-yl)propanoate

To a solution containing (2S,3S)-3-phenylbutan-2-yl(3-hydroxy-4-methoxypicolinoyl)-L-alaninate (54 mg, 0.15 mmol) andtriphosgene (86 mg, 0.29 mmol) dissolved in methylene chloride (1.0 mL)was added pyridine (0.1 mL, 1.24 mmol). Upon stirring for 45 min, thereaction mixture was quenched with saturated sodium bicarbonate solution(5 mL) and extracted with methylene chloride (3×5 mL). The organics werepassed through a phase separator and concentrated in vacuo. The cruderesidue was purified via automated flash column chromatography (SiO₂,0-40% acetone/hexanes gradient) to afford (2S,3S)-3-phenylbutan-2-yl(S)-2-(8-methoxy-2,4-dioxo-2H-pyrido[2,3-e][1,3]oxazin-3(4H)-yl)propanoate(41 mg, 0.10 mmol, 67% yield) as an off-white foam: ¹H NMR (500 MHz,CDCl₃) δ 8.61 (d, J=5.3 Hz, 1H), 7.24-7.17 (m, 2H), 7.17-7.06 (m, 4H),5.61 (q, J=7.1 Hz, 1H), 5.16-5.06 (m, 1H), 4.06 (s, 3H), 2.93-2.83 (m,1H), 1.70 (d, J=7.1 Hz, 3H), 1.27 (d, J=7.1 Hz, 3H), 1.04 (d, J=6.3 Hz,3H); IR (thin film) 2978, 2942, 1769, 1712, 1602, 1501, 1371, 1242,1081, 702 cm⁻¹; HRMS-ESI (m/z) [M+H]+ calc'd for C₂₁H₂₃N₂O₆, 399.1551;found, 399.1549.

Example A: Evaluation of Fungicidal Activity: Leaf Blotch of Wheat(Zymoseptoria tritici; Bayer Code SEPTTR)

Technical grades of materials were dissolved in acetone, which were thenmixed with nine volumes of water containing 110 ppm Triton X-100. Thefungicide solutions were applied onto wheat seedlings using an automatedbooth sprayer to run-off. All sprayed plants were allowed to air dryprior to further handling. All fungicides were evaluated using theaforementioned method for their activity vs. all target diseases, unlessstated otherwise. Wheat leaf blotch and brown rust activity were alsoevaluated using track spray applications, in which case the fungicideswere formulated as EC formulations, containing 0.1% Trycol 5941 in thespray solutions.

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50%mineral soil/50% soil-less Metro mix until the first leaf was fullyemerged, with 7-10 seedlings per pot. These plants were inoculated withan aqueous spore suspension of Zymoseptoria tritici either prior to orafter fungicide treatments. After inoculation the plants were kept in100% relative humidity (one day in a dark dew chamber followed by two tothree days in a lighted dew chamber at 20° C.) to permit spores togerminate and infect the leaf. The plants were then transferred to agreenhouse set at 20° C. for disease to develop. When disease symptomswere fully expressed on the 1^(st) leaves of untreated plants, infectionlevels were assessed on a scale of 0 to 100 percent disease severity.Percent disease control was calculated using the ratio of diseaseseverity on treated plants relative to untreated plants.

Example B: Evaluation of Fungicidal Activity: Wheat Brown Rust (Pucciniatriticina; Synonym: Puccinia recondita f. sp. tritici; Bayer CodePUCCRT)

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50%mineral soil/50% soil-less Metro mix until the first leaf was fullyemerged, with 7-10 seedlings per pot. These plants were inoculated withan aqueous spore suspension of Puccinia triticina either prior to orafter fungicide treatments. After inoculation the plants were kept in adark dew room at 22° C. with 100% relative humidity overnight to permitspores to germinate and infect the leaf. The plants were thentransferred to a greenhouse set at 24° C. for disease to develop.Fungicide formulation, application and disease assessment followed theprocedures as described in the Example A.

Example C: Evaluation of Fungicidal Activity: Asian Soybean Rust(Phakopsora pachyrhizi; Bayer Code PHAKPA)

Technical grades of materials were dissolved in acetone, which were thenmixed with nine volumes of water containing 0.011% Tween 20. Thefungicide solutions were applied onto soybean seedlings using anautomated booth sprayer to run-off. All sprayed plants were allowed toair dry prior to further handling.

Soybean plants (variety Williams 82) were grown in soil-less Metro mix,with one plant per pot. Two week old seedlings were used for testing.Plants were inoculated either 3 days prior to or 1 day after fungicidetreatments. Plants were incubated for 24 h in a dark dew room at 22° C.and 100% relative humidity then transferred to a growth room at 23° C.for disease to develop. Disease severity was assessed on the sprayedleaves.

Example D: Evaluation of Fungicidal Activity: Tomato Early Blight(Alternaria solani; Bayer Code ALTESO)

Tomato plants (variety Outdoor Girl) were propagated in soil-less Metromix, with each pot having one plant, and used when 12 to 14 days old.Test plants were inoculated with an aqueous spore suspension ofAlternaria solani 24 hr after fungicide treatments. After inoculationthe plants were kept in 100% relative humidity (one day in a dark dewchamber followed by two to three days in a lighted dew chamber at 20°C.) to permit spores to germinate and infect the leaf. The plants werethen transferred to a growth room at 22° C. for disease to develop.Fungicide formulation, application and disease assessment on the sprayedleaves followed the procedures as described in the Example A.

Example E: Evaluation of Fungicidal Activity: Leaf Spot of Sugar Beets(Cercospora beticola; Bayer Code CERCBE)

Sugar beet plants (variety HH88) were grown in soil-less Metro mix andtrimmed regularly to maintain a uniform plant size prior to test. Plantswere inoculated with a spore suspension 24 hr after fungicidetreatments. Inoculated plants were kept in a dew chamber at 22° C. for48 hr then incubated in a greenhouse set at 24° C. under a clear plastichood with bottom ventilation until disease symptoms were fullyexpressed. Fungicide formulation, application and disease assessment onthe sprayed leaves followed the procedures as described in the ExampleA.

Example F: Evaluation of Fungicidal Activity: Cucumber Anthracnose(Glomerella lagenarium; Anamorph: Colletotrichum lagenarium; Bayer CodeCOLLLA)

Cucumber seedlings (variety Bush Pickle) were propagated in soil-lessMetro mix, with each pot having one plant, and used in the test when 12to 14 days old. Test plants were inoculated with an aqueous sporesuspension of Colletotrichum lagenarium 24 hr after fungicidetreatments. After inoculation the plants were kept in a dew room at 22°C. with 100% relative humidity for 48 hr to permit spores to germinateand infect the leaf. The plants were then transferred to a growth roomset at 22° C. for disease to develop. Fungicide formulation, applicationand disease assessment on the sprayed leaves followed the procedures asdescribed in the Example A.

Example G: Evaluation of Fungicidal Activity: Wheat Glume Blotch(Parastagonospora nodorum; Bayer Code LEPTNO)

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50%mineral soil/50% soil-less Metro mix until the first leaf was fullyemerged, with 7-10 seedlings per pot. These plants were inoculated withan aqueous spore suspension of Parastagonospora nodorum 24 hr afterfungicide treatments. After inoculation the plants were kept in 100%relative humidity (one day in a dark dew chamber followed by two days ina lighted dew chamber at 20° C.) to permit spores to germinate andinfect the leaf. The plants were then transferred to a greenhouse set at20° C. for disease to develop. Fungicide formulation, application anddisease assessment followed the procedures as described in the ExampleA.

Example H: Evaluation of Fungicidal Activity: Cucumber Downy Mildew(Pseudoperonospora cubensis; Bayer Code PSPECU)

Cucumber seedlings (variety Bush Pickle) were grown in soil-less Metromix, with one plant per pot, and used in the test when 12 to 14 daysold. Plants were inoculated with a spore suspension 24 hr followingfungicide treatments. Test plants were inoculated with an aqueous sporesuspension of Pseudoperonospora cubensis 24 hr after fungicidetreatments. After inoculation the plants were kept in a dew room at 22°C. with 100% relative humidity for 24 hr to permit spores to germinateand infect the leaf. The plants were then transferred to a greenhouseset at 20° C. until disease was fully expressed. Fungicide formulation,application and disease assessment on the sprayed leaves followed theprocedures as described in the Example A.

Example I: Evaluation of Fungicidal Activity: Rice Blast (Magnaporthegrisea; Anamorph: Pyricularia oryzae; Bayer Code PYRIOR)

Rice seedlings (variety Japonica) were propagated in soil-less Metromix, with each pot having 8 to 14 plants, and used in the test when 12to 14 days old. Test plants were inoculated with an aqueous sporesuspension of Pyricularia oryzae 24 hr after fungicide treatments. Afterinoculation, the plants were kept in a dew room at 22° C. with 100%relative humidity for 48 hr to permit spores to germinate and infect theleaf. The plants were then transferred to a greenhouse set at 24° C. fordisease to develop. Fungicide formulation, application and diseaseassessment on the sprayed leaves followed the procedures as described inthe Example A.

Example J: Evaluation of Fungicidal Activity: Barley Scald(Rhyncosporium secalis; Bayer Code RHYNSE)

Barley seedlings (variety Harrington) were propagated in soil-less Metromix, with each pot having 8 to 12 plants, and used in the test whenfirst leaf was fully emerged. Test plants were inoculated by an aqueousspore suspension of Rhyncosporium secalis 24 hr after fungicidetreatments. After inoculation the plants were kept in a dew room at 20°C. with 100% relative humidity for 48 hr. The plants were thentransferred to a greenhouse set at 20° C. for disease to develop.Fungicide formulation, application and disease assessment on the sprayedleaves followed the procedures as described in the Example A.

Example K: Evaluation of Fungicidal Activity: Grape Powdery Mildew(Uncinula necator; Bayer Code UNCINE)

Grape seedlings (variety Carignane) were grown in soil-less Metro mix,with one plant per pot, and used in the test when approximately 1 monthold. Plants were inoculated 24 hr after fungicide treatment by shakingspores from infected leaves over test plants. Plants were maintained ina greenhouse set at 20° C. until disease was fully developed. Fungicideformulation, application and disease assessment on sprayed leavesfollowed the procedures as described in the Example A.

TABLE 1 Compound Structure, Appearance, and Preparation Method AsPrepared Cmpd. According No. Structure To Appearance 1

Example 1A Example 2 Example 3 Oil 2

Example 1A Example 2 Example 3 Oil 3

Example 1A Example 2 Example 3 Oil 4

Example 1A Example 2 Example 3 Oil 5

Example 1A Example 2 Example 3 Oil 6

Example 1A Example 2 Example 3 Oil 7

Example 1A Example 2 Example 3 Oil 8

Example 1A Example 2 Example 3 Oil 9

Example 1B Example 2 Example 3 Oil 10

Example 1B Example 2 Example 3 Oil 11

Example 1B Example 2 Example 3 Oil 12

Example 1B Example 2 Example 3 Oil 13

Example 1B Example 2 Example 3 Oil 14

Example 1B Example 2 Example 3 Oil 15

Example 1B Example 2 Example 3 Oil 16

Example 1B Example 2 Example 3 Oil 17

Example 1B Example 2 Example 3 Oil 18

Example 1B Example 2 Example 3 Oil 19

Example 1B Example 2 Example 3 Oil 20

Example 1B Example 2 Example 3 Oil 21

Example 1B Example 2 Example 3 Oil 22

Example 1A Example 2 Example 3 Oil 23

Example 1A Example 2 Example 3 Oil 24

Example 1A Example 2 Example 3 Oil 25

Example 1A Example 2 Example 3 Oil 26

Example 1A Example 2 Example 3 Oil 27

Example 1A Example 2 Example 3 Oil 28

Example 1A Example 2 Example 3 Oil 29

Example 1B Example 2 Example 3 Oil 30

Example 1B Example 2 Example 3 Oil 31

Example 1B Example 2 Example 3 Oil 32

Example 1B Example 2 Example 3 Oil 33

Example 1B Example 2 Example 3 Oil 34

Example 1B Example 2 Example 3 Oil 35

Example 1B Example 2 Example 3 Oil 36

Example 1B Example 2 Example 3 Oil 37

Example 1B Example 2 Example 3 Oil 38

Example 1B Example 2 Example 3 Oil 39

Example 1B Example 2 Example 3 Oil 40

Example 1B Example 2 Example 3 Oil 41

Example 1A Example 2 Example 3 Light Yellow Oil 42

Example 1A Example 2 Example 3 Clear Oil 43

Example 1A Example 2 Example 3 Reddish Brown Oil 44

Example 1A Example 2 Example 3 Orange Oil 45

Example 1A Example 2 Example 3 Yellow Oil 46

Example 1A Example 2 Example 3 Yellow Oil 47

Example 1A Example 3 Clear, Colorless Oil 48

Example 1A Example 3 Pale Yellow Oil 49

Example 1A Example 2 Example 3 Clear, Colorless Oil 50

Example 1A Example 2 Example 3 Pale Yellow Oil 51

Example 1A Example 2 Example 3 Clear, Colorless Oil 52

Example 1A Example 2 Example 3 Clear, Colorless Oil 53

Example 1B Example 2 Example 3 Colorless Oil 54

Example 1C Example 2 Example 3 Colorless Oil 55

Example 1B Example 2 Example 3 Yellow Oil 56

Example 1B Example 2 Example 3 Colorless Oil 57

Example 1B Example 2 Example 3 Residue 58

Example 4 Step 1 Oil 59

Example 4 Step 1 Oil 60

Example 4 Step 1 Oil 61

Example 4 Step 1 Oil 62

Example 4 Step 1 Oil 63

Example 4 Step 1 Oil 64

Example 4 Step 1 Oil 65

Example 4 Step 1 Oil 66

Example 4 Step 1 Oil 67

Example 4 Step 1 Oil 68

Example 4 Step 1 Oil 69

Example 4 Step 1 Oil 70

Example 4 Step 1 Oil 71

Example 4 Step 1 Oil 72

Example 4 Step 1 Oil 73

Example 4 Step 1 Oil 74

Example 4 Step 1 Oil 75

Example 4 Step 1 Oil 76

Example 4 Step 1 Oil 77

Example 4 Step 1 Oil 78

Example 4 Step 1 Oil 79

Example 4 Step 1 Oil 80

Example 4 Step 1 Oil 81

Example 4 Step 1 Oil 82

Example 4 Step 1 Oil 83

Example 4 Step 1 Oil 84

Example 4 Step 1 Oil 85

Example 4 Step 1 Oil 86

Example 4 Step 1 Oil 87

Example 4 Step 1 Oil 88

Example 4 Step 1 Oil 89

Example 4 Step 1 Oil 90

Example 4 Step 1 Oil 91

Example 4 Step 1 Oil 92

Example 4 Step 1 Oil 93

Example 4 Step 1 Oil 94

Example 4 Step 1 Oil 95

Example 4 Step 1 Oil 96

Example 4 Step 1 Oil 97

Example 4 Step 1 Oil 98

Example 4 Step 1 Dark Yellow Oil 99

Example 4 Step 1 Dark Yellow Oil 100

Example 4 Step 1 Brown Semisolid 101

Example 4 Step 1 Light Brown Semisolid 102

Example 1A Example 2 Example 3 Example 4 Step 1 Pale Yellow Oil 103

Example 4 Step 1 Orange Semisolid 104

Example 4 Step 1 Orange Semisolid 105

Example 1A Example 2 Example 3 Example 4 Step 1 White Semisolid 106

Example 4 Step 1 White Semisolid 107

Example 4 Step 1 Pale Yellow Oil 108

Example 4 Step 1 White Semisolid 109

Example 4 Step 1 Clear, Colorless Glass 110

Example 4 Step 1 Clear, Colorless Oil 111

Example 4 Step 1 Clear, Colorless Oil 112

Example 4 Step 1 Colorless Oil 113

Example 4 Step 1 White Solid 114

Example 4 Step 1 Yellow Oil 115

Example 4 Step 1 Colorless Oil 116

Example 4 Step 2 Thick Clear Oil 117

Example 4 Step 2 Thick Clear Oil 118

Example 4 Step 2 White Solid 119

Example 4 Step 2 White Solid 120

Example 4 Step 2 Thick Oil 121

Example 4 Step 2 Thick Oil 122

Example 4 Step 2 Thick Oil 123

Example 4 Step 2 White Solid 124

Example 4 Step 2 Thick Oil 125

Example 4 Step 2 Thick Oil 126

Example 4 Step 2 White Solid 127

Example 4 Step 2 Thick Oil 128

Example 4 Step 2 White Solid 129

Example 4 Step 2 Thick Oil 130

Example 4 Step 2 White Solid 131

Example 4 Step 2 Thick Oil 132

Example 4 Step 2 Thick Oil 133

Example 4 Step 2 Thick Oil 134

Example 4 Step 2 Thick Oil 135

Example 4 Step 2 Think Oil 136

Example 4 Step 2 Thick Oil 137

Example 4 Step 2 Thick Oil 138

Example 4 Step 2 White Solid 139

Example 4 Step 2 Thick Oil 140

Example 4 Step 2 Thick Oil 141

Example 4 Step 2 White Solid 142

Example 4 Step 2 Thick Oil 143

Example 4 Step 2 Thick Oil 144

Example 4 Step 2 Thick Oil 145

Example 4 Step 2 Think Oil 146

Example 4 Step 2 Thick Oil 147

Example 4 Step 2 Thick Oil 148

Example 4 Step 2 Thick Oil 149

Example 4 Step 2 Thick Oil 150

Example 4 Step 2 Thick Oil 151

Example 4 Step 2 Thick Oil 152

Example 4 Step 2 Thick Oil 153

Example 4 Step 2 White Solid 154

Example 4 Step 2 Thick Oil 155

Example 4 Step 2 White Solid 156

Example 4 Step 2 Thick Oil 157

Example 4 Step 2 Thick Oil 158

Example 4 Step 2 Orange Oil 159

Example 4 Step 2 Orange Oil 160

Example 4 Step 2 Pale Yellow Oil 161

Example 4 Step 2 Yellow Oil 162

Example 4 Step 2 Yellow Oil 163

Example 4 Step 2 Clear, Colorless Oil 164

Example 4 Step 2 Yellow Oil 165

Example 4 Step 2 Orange Oil 166

Example 4 Step 2 Clear, Colorless Oil 167

Example 4 Step 2 Yellow Oil 168

Example 4 Step 2 Clear, Colorless Oil 169

Example 4 Step 2 Yellow Oil 170

Example 4 Step 2 Colorless Oil 171

Example 4 Step 2 Colorless Oil 172

Example 4 Step 2 Pale Yellow Oil 173

Example 4 Step 2 Colorless Oil 174

Example 4 Step 2 Clear Oil 175

Example 4 Step 2 Colorless Foam 176

Example 4 Step 2 Residue 177

Example 5A Thick Oil 178

Example 5A Thick Oil 179

Example 5C Thick Oil 180

Example 5C Thick Oil 181

Example 5A Thick Oil 182

Example 5A Thick Oil 183

Example 5A Thick Oil 184

Example 5A Thick Oil 185

Example 5A Thick Oil 186

Example 5A Thick Oil 187

Example 5A Thick Oil 188

Example 5A Thick Oil 189

Example 5A Thick Oil 190

Exampel 5A Thick Oil 191

Example 5A Thick Oil 192

Example 5A Thick Oil 193

Example 5A Thick Oil 194

Example 5A Thick Oil 195

Example 5A Thick Oil 196

Example 5C Thick Oil 197

Example 5C Thick Oil 198

Example 5C Thick Oil 199

Example 5C Thick Oil 200

Example 5C Thick Oil 201

Example 5C Thick Oil 202

Example 5C Thick Oil 203

Example 5C Thick Oil 204

Example 5C Thick Oil 205

Example 5C Thick Oil 206

Example 5C Thick Oil 207

Example 5C Thick Oil 208

Example 5C Thick Oil 209

Example 5C Thick Oil 210

Example 5C Thick Oil 211

Example 5C Thick Oil 212

Example 5C Thick Oil 213

Example 5C Thick Oil 214

Example 5C Thick Oil 215

Example 5C Thick Oil 216

Example 5C Thick Oil 217

Example 5C Thick Oil 218

Example 5C Thick Oil 219

Example 5C Thick Oil 220

Example 5A Thick Oil 221

Example 5C Thick Oil 222

Example 5C Thick Oil 223

Example 5C Thick Oil 224

Example 5C Thick Oil 225

Example 5C Thick Oil 226

Example 5C Thick Oil 227

Example 5C Thick Oil 228

Example 5C Thick Oil 229

Example 5C Thick Oil 230

Example 5C Thick Oil 231

Example 5B Thick Oil 232

Example 5B Thick Oil 233

Example 5B Thick Oil 234

Example 5C Yellow Oil 235

Example 5C Pale Yellow Oil 236

Example 5C Yellow Oil 237

Example 5C Clear, Colorless Oil 238

Example 5C Clear, Colorless Oil 239

Example 5C Clear, Colorless Oil 240

Example 5C Clear, Colorless Oil 241

Example 5C Clear, Colorless Oil 242

Example 5C Clear, Colorless Oil 243

Example 5C Clear, Colorless Oil 244

Example 5C Clear, Colorless Oil 245

Example 5C Yellow Oil 246

Example 5C Pale Yellow Oil 247

Example 5C Clear, Colorless Oil 248

Example 5C Clear, Colorless Oil 249

Example 5C Clear, Colorless Oil 250

Example 5C Clear, Colorless Oil 251

Example 5C Clear, Colorless Oil 252

Example 5C Clear, Colorless Oil 253

Example 5C Clear, Colorless Oil 254

Example 5C Clear, Colorless Oil 255

Example 5C Clear, Colorless Oil 256

Example 5C Clear, Colorless Oil 257

Example 5A Colorless Oil 258

Example 5A Colorless Oil 259

Example 5A Pale Yellow Oil 260

Example 5A Colorless Oil 261

Example 8 Off-White Foam 262

Example 8 Tan Foam 263

Example 5A Clear Oil 264

Example 5A Clear Oil 265

Example 5C Clear Oil 266

Example 5C Colorless Oil 267

Example 6 Step 1 Yellow Semisolid 268

Example 6 Step 1 Yellow Semisolid 269

Example 6 Step 1 Orange Semisolid 270

Example 6 Step 2 Yellow Oil 271

Example 6 Step 2 Yellow Oil 272

Example 6 Step 2 Yellow Oil 273

Example 7 Yellow Oil 274

Example 7 Pale Yellow Oil 275

Example 7 Pale Yellow Oil 276

Example 7 Pale Yellow Oil 277

Example 7 Pale Yellow Oil 278

Example 5C White Solid 279

Example 5C White Solid 280

Example 5C Yellow Oil 281

Example 5C Clear Oil 282

Example 5C White Solid 284

Example 5C Thick Yellow Oil 285

Example 5C Glassy Solid *Cmpd. No.-Compound Number

TABLE 2 Analytical Data Melting Cmpd. Point No. (° C.) IR (cm⁻¹) MASSSPEC NMR 1 ESIMS m/z 362.3 ([M + Na]⁺) 2 ESIMS m/z 354.3 ([M + H]⁺) 3ESIMS m/z 382.3 ([M + H]⁺) 4 ESIMS m/z 376.3 ([M + Na]⁺) 5 ESIMS m/z362.3 ([M + Na]⁺) 6 ESIMS m/z 354.3 ([M + H]⁺) 7 ESIMS m/z 382.3 ([M +H]⁺) 8 ESIMS m/z 354.3 ([M + H]⁺) 9 ESIMS m/z 344.3 ([M + Na]⁺) 10 ESIMSm/z 336.5 ([M + H]⁺) 11 ESIMS m/z 364.3 ([M + H]⁺) 12 ESIMS m/z 336.2([M + H]⁺) 13 ESIMS m/z 348.2 ([M + Na]⁺) 14 ESIMS m/z 340.5 ([M + H]⁺)15 ESIMS m/z 390.3 ([M + Na]⁺) 16 ESIMS m/z 340.2 ([M + H]⁺) 17 ESIMSm/z 374.3 ([M + Na]⁺) 18 ESIMS m/z 366.3 ([M + H]⁺) 19 ESIMS m/z 394.3([M + H]⁺) 20 ESIMS m/z 366.3 ([M + H]⁺) 21 ESIMS m/z 362.3 ([M + Na]⁺)22 ESIMS m/z 376.3 ([M + Na]⁺) 23 ESIMS m/z 382.3 ([M + H]⁺) 24 ESIMSm/z 354.3 ([M + H]⁺) 25 ESIMS m/z 362.3 ([M + Na]⁺) 26 ESIMS m/z 376.3([M + Na]⁺) 27 ESIMS m/z 382.3 ([M + H]⁺) 28 ESIMS m/z 376.3 ([M + Na]⁺)29 ESIMS m/z 344.3 ([M + Na]⁺) 30 ESIMS m/z 336.2 ([M + H]⁺) 31 ESIMSm/z 364.3 ([M + H]⁺) 32 ESIMS m/z 336.3 ([M + H]⁺) 33 ESIMS m/z 348.2([M + Na]⁺) 34 ESIMS m/z 340.3 ([M + H]⁺) 35 ESIMS m/z 368.3 ([M + H]⁺)36 ESIMS m/z 340.3 ([M + H]⁺) 37 ESIMS m/z 374.3 ([M + Na]⁺) 38 ESIMSm/z 366.3 ([M + H]⁺) 39 ESIMS m/z 394.4 ([M + H]⁺) 40 ESIMS m/z 366.3([M + H]⁺) 41 ESIMS m/z 372.3 ([M + Na]⁺) 42 ESIMS m/z 372.3 ([M + Na]⁺)43 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 3355, [M +Na]⁺ calcd for 7.64 (dd, J = 7.8, 1.4 Hz, 1H), 7.52 (td, J = 7.6, 2981,1711, C₁₉H₂₆F₃NNaO₄, 1.3 Hz, 1H), 7.43 (d, J = 7.9 Hz, 1310, 1150,412.1706; found, 1H), 7.35-7.28 (m, 1H), 1116, 1046, 412.1698 5.25-5.13(m, 1H), 5.08 (d, J = 7.9 Hz, 1H), 770 cm⁻¹ 4.42-4.28 (m, 1H), 3.41-3.27(m, 1H), 1.46 (s, 9H), 1.43 (d, J = 7.2 Hz, 3H), 1.27 (d, J = 6.8 Hz,3H), 1.07 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.25. 44 IR(thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 3362, [M + Na]⁺calcd for 7.42 (dd, J = 8.8, 5.4 Hz, 1H), 7.35 (dd, J = 9.2, 2982, 1711,C₁₉H₂₅F₄NNaO₄, 2.8 Hz, 1H), 7.23 (td, J = 8.2, 2.8 Hz, 1499, 1314,430.1612; found, 1H), 5.18-5.09 (m, 1H), 5.07 (d, 1154, 1121, 430.1607 J= 7.6 Hz, 1H), 4.41-4.27 (m, 1H), 1046, 909, 3.36-3.24 (m, 1H), 1.46 (s,9H), 879 cm⁻¹ 1.42 (d, J = 7.3 Hz, 3H), 1.26 (d, J = 6.8 Hz, 3H), 1.08(d, J = 6.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.81, −114.05. 45 IR(thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 3364, [M + Na]⁺calcd for 7.64 (dd, J = 8.0, 1.3 Hz, 1H), 7.52 (td, J = 7.6, 2981, 1712,C₁₉H₂₆F₃NNaO₄, 1.3 Hz, 1H), 7.43 (d, J = 7.8 Hz, 1310, 1150, 412.1706;found, 1H), 7.32 (t, J = 7.6 Hz, 1H), 1116, 1046, 412.1699 5.25-5.13 (m,1H), 5.04 (d, J = 7.8 Hz, 1H), 770 cm⁻¹ 4.42-4.26 (m, 1H), 3.40-3.26 (m,1H), 1.46 (s, 9H), 1.41 (d, J = 7.3 Hz, 3H), 1.29 (d, J = 6.7 Hz, 3H),1.05 (d, J = 6.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.25. 46 IR (thinHRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 2981, [M + Na]⁺ calcd for7.42 (dd, J = 8.8, 5.3 Hz, 1H), 7.35 (dd, J = 9.2, 1711, 1498,C₁₉H₂₅F₄NNaO₄, 2.8 Hz, 1H), 7.23 (td, J = 8.3, 2.9 Hz, 1314, 1154,430.1612; found, 1H), 5.20-5.09 (m, 1H), 5.02 (d, 1120, 1045, 430.1603 J= 7.8 Hz, 1H), 4.42-4.23 (m, 1H), 909, 879, 3.29 (tt, J = 7.6, 6.0 Hz,1H), 1.46 (s, 739 cm⁻¹ 9H), 1.40 (d, J = 7.2 Hz, 3H), 1.28 (d, J = 6.8Hz, 3H), 1.07 (d, J = 6.4 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.78,−58.80, −114.19. 47 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δfilm) 3357, [M + NH₄]⁺ calcd 7.05-6.91 (m, 3H), 5.58 (ddq, J = 10.5,8.3, 2977, 1713, for C₂₀H₃₅N₂O₄, 6.2 Hz, 1H), 5.11 (s, 1H), 1500, 1452,367.2587; found, 4.42-4.28 (m, 1H), 3.49-3.33 (m, 1H), 1365, 1162,367.2587 2.44-2.33 (m, 6H), 1.46 (d, J = 1.1 Hz, 9H), 1055, 1006,1.45-1.39 (m, 3H), 1.27 (dd, J = 7.1, 769 cm⁻¹ 3.5 Hz, 3H), 1.02 (dd, J= 7.7, 6.2 Hz, 3H). 48 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δfilm) 3357, [M + Na]⁺ calcd for 6.70 (ddd, J = 16.1, 9.4, 2.9 Hz, 2H),2978, 1712, C₂₀H₃₀FNNaO₄, 5.53 (ddq, J = 10.5, 8.6, 6.2 Hz, 1H), 1366,1162, 390.2051; found, 5.11 (s, 1H), 4.41-4.26 (m, 1H), 1057, 1023,390.2048 3.44-3.27 (m, 1H), 2.40 (d, J = 1.7 Hz, 3H), 1006, 857 cm⁻¹2.35 (s, 3H), 1.46 (s, 9H), 1.45-1.38 (m, 3H), 1.25 (dd, J = 7.2, 3.8Hz, 3H), 1.01 (dd, J = 7.6, 6.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ−118.37, −118.44. 49 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δfilm) 3361, [M + Na]⁺ calcd for 7.04-6.93 (m, 3H), 5.58 (ddq, J = 10.4,8.3, 2977, 1713, C₂₀H₃₁NNaO₄, 6.2 Hz, 1H), 5.10 (d, J = 7.3 Hz, 1H),1365, 1162, 372.2145; found, 4.43-4.27 (m, 1H), 3.48-3.29 (m, 1056,1006, 372.2144 1H), 2.41 (d, J = 1.6 Hz, 3H), 2.37 (s, 769 cm⁻¹ 3H),1.46 (d, J = 1.1 Hz, 9H), 1.45-1.39 (m, 3H), 1.27 (dd, J = 7.1, 3.5 Hz,3H), 1.02 (dd, J = 7.7, 6.2 Hz, 3H). 50 IR (thin HRMS-ESI (m/z) ¹H NMR(400 MHz, CDCl₃) δ film) 3359, [M + Na]⁺ calcd for 6.70 (ddd, J = 16.2,9.4, 2.9 Hz, 2H), 2978, 1712, C₂₀H₃₀FNNaO₄, 5.53 (ddq, J = 10.5, 8.6,6.2 Hz, 1H), 1450, 1366, 390.2051; found, 5.09 (s, 1H), 4.43-4.28 (m,1H), 3.34 (dp, 1163, 1057, 390.2050 J = 10.3, 6.9 Hz, 1H), 2.40 (d, J =1.7 Hz, 1023, 1006, 3H), 2.35 (s, 3H), 1.46 (s, 9H), 858, 732 cm⁻¹1.45-1.36 (m, 3H), 1.26 (d, J = 3.8 Hz, 3H), 1.01 (dd, J = 7.6, 6.2 Hz,3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −118.40, −118.46. 51 IR (thin HRMS-ESI(m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 3356, [M + Na]⁺ calcd for7.03-6.94 (m, 3H), 5.58 (ddq, J = 10.5, 8.3, 2977, 1713, C₂₀H₃₁NNaO₄,6.2 Hz, 1H), 5.10 (d, J = 7.1 Hz, 1H), 1500, 1452, 372.2145; found,4.43-4.27 (m, 1H), 3.50-3.34 (m, 1163, 1056, 372.2137 1H), 2.41 (d, J =1.6 Hz, 3H), 2.37 (s, 769 cm⁻¹ 3H), 1.46 (d, J = 1.1 Hz, 9H), 1.45-1.36(m, 3H), 1.27 (dd, J = 7.2, 3.5 Hz, 3H), 1.02 (dd, J = 7.7, 6.2 Hz, 3H).52 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 3358, [M +Na]⁺ calcd for 6.70 (ddd, J = 16.0, 9.4, 2.9 Hz, 2H), 2978, 1712,C₂₀H₃₀FNNaO₄, 5.53 (ddq, J = 10.5, 8.5, 6.2 Hz, 1H), 1366, 1163,390.2051; found, 5.11 (s, 1H), 4.33 (q, J = 7.3 Hz, 1H), 1058, 1023,390.2051 3.35 (ddq, J = 13.0, 10.4, 7.1, 6.5 Hz, 1H), 1006, 858, 2.40(d, J = 1.8 Hz, 3H), 2.35 (s, 3H), 733 cm⁻¹ 1.46 (s, 9H), 1.45-1.39 (m,3H), 1.25 (dd, J = 7.2, 3.8 Hz, 3H), 1.01 (dd, J = 7.6, 6.2 Hz, 3H). ¹⁹FNMR (376 MHz, CDCl₃) δ −118.39, −118.45. 53 IR (thin HRMS-ESI (m/z) ¹HNMR (400 MHz, CDCl₃) δ film) 3357, [M + Na]⁺ calcd for 7.23-7.12 (m,2H), 6.96-6.79 (m, 2H), 2977, 2936, C₁₉H₂₉NO₅Na, 5.24 (dq, J = 7.7, 6.3Hz, 1H), 5.00 (d, J = 6.6 Hz, 2837, 1711, 374.1938; found, 1H),4.19-4.10 (m, 1H), 1493, 1241, 374.1944 3.81 (s, 3H), 3.43 (p, J = 7.3Hz, 1H), 1161, 1052, 1.42 (s, 9H), 1.25-1.20 (m, 6H), 0.99 (d, J = 7.1Hz, 752 cm⁻¹ 3H). 54 IR (thin ¹H NMR (400 MHz, CDCl₃) δ film) 3355,7.35-7.25 (m, 2H), 7.27-7.15 (m, 3H), 2978, 2934, 5.12-5.01 (m, 2H),4.35-4.26 (m, 1H), 1711, 1495, 2.95-2.83 (m, 1H), 1.45 (s, 9H), 1452,1366, 1.37 (d, J = 7.2 Hz, 3H), 1.29 (d, J = 7.1 Hz, 1161, 1087, 3H),1.09 (d, J = 6.3 Hz, 3H). 1065, 701 cm⁻¹ ¹³C NMR (126 MHz, CDCl₃) δ172.9, 155.0, 143.0, 128.5, 127.8, 126.7, 79.7, 76.1, 49.5, 45.1, 28.3,18.9, 18.3, 17.5. 55 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δfilm) 3365, [M + Na]⁺ calcd for 6.64-6.53 (m, 2H), 5.11-5.05 (m, 1H),2977, 2933, C₁₇H₂₇NO₄SNa, 5.06-4.95 (m, 1H), 4.35-4.26 (m, 1H), 1712,1500, 364.1553; found, 3.20-3.08 (m, 1H), 2.43 (d, J = 1.2 Hz, 1449,1365, 364.1551 3H), 1.45 (s, 9H), 1.38 (d, J = 7.2 Hz, 1161, 1065, 3H),1.31 (d, J = 7.1 Hz, 3H), 796 cm⁻¹ 1.16 (d, J = 6.3 Hz, 3H). 56 IR (thinHRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ film) 3365, [M + Na]⁺ calcd for7.08 (dd, J = 8.5, 6.7 Hz, 1H), 2978, 2937, C₁₉H₂₈FNO₅Na, 6.65-6.53 (m,2H), 5.16-5.07 (m, 1H), 5.05 (d, J = 7.6 Hz, 1708, 1601, 392.1844;found, 1H), 4.30-4.23 (m, 1H), 1502, 1163, 392.1839 3.80 (s, 3H),3.38-3.29 (m, 1H), 1035, 952, 1.45 (s, 9H), 1.35 (d, J = 7.2 Hz, 3H),834 cm⁻¹ 1.23 (d, J = 7.1 Hz, 3H), 1.10 (d, J = 6.3 Hz, 3H). 57 ¹H NMR(300 MHz, CDCl₃) δ 7.13-6.95 (m, 2H), 6.77-6.52 (m, 2H), 5.11 (d, J =7.8 Hz, 1H), 5.00 (dq, J = 8.2, 6.2 Hz, 1H), 4.31 (t, J = 7.4 Hz, 1H),2.92 (s, 6H), 1.45 (s, 9H), 1.39 (d, J = 7.2 Hz, 3H), 1.31-1.17 (m, 4H),1.08 (d, J = 6.3 Hz, 3H). ¹³C NMR (75 MHz, CDCl₃) δ 172.95, 171.16,155.04, 149.48, 130.86, 128.41, 112.69, 60.40, 49.51, 44.14, 40.70,28.35, 18.93, 18.27, 17.82, 14.21. 58 ESIMS m/z 240.2 ([M + H]⁺) 59ESIMS m/z 240.2 ([M + H]⁺) 60 ESIMS m/z 222.2 ([M + H]⁺) 61 ESIMS m/z248.9 ([M + Na]⁺) 62 ESIMS m/z 252.2 ([M + H]⁺) 63 ESIMS m/z 240.2 ([M +H]⁺) 64 ESIMS m/z 240.2 ([M + H]⁺) 65 ESIMS m/z 222.2 ([M + H]⁺) 66ESIMS m/z 226.2 ([M + H]⁺) 67 ESIMS m/z 252.2 ([M + H]⁺) 68 ESIMS m/z254.2 ([M + H]⁺) 69 ESIMS m/z 254.2 ([M + H]⁺) 70 ESIMS m/z 236.2 ([M +H]⁺) 71 ESIMS m/z 240.2 ([M + H]⁺) 72 ESIMS m/z 266.3 ([M + H]⁺) 73ESIMS m/z 254.2 ([M + H]⁺) 74 ESIMS m/z 254.2 ([M + H]⁺) 75 ESIMS m/z236.2 ([M + H]⁺) 76 ESIMS m/z 240.2 ([M + H]⁺) 77 ESIMS m/z 266.3 ([M +H]⁺) 78 ESIMS m/z 282.3 ([M + H]⁺) 79 ESIMS m/z 282.2 ([M + H]⁺) 80ESIMS m/z 264.3 ([M + H]⁺) 81 ESIMS m/z 268.2 ([M + H]⁺) 82 ESIMS m/z294.3 ([M + H]⁺) 83 ESIMS m/z 282.2 ([M + H]⁺) 84 ESIMS m/z 282.2 ([M +H]⁺) 85 ESIMS m/z 264.3 ([M + H]⁺) 86 ESIMS m/z 268.2 ([M + H]⁺) 87ESIMS m/z 294.3 ([M + H]⁺) 88 ESIMS m/z 254.2 ([M + H]⁺) 89 ESIMS m/z254.2 ([M + H]⁺) 90 ESIMS m/z 236.2 ([M + H]⁺) 91 ESIMS m/z 240.2 ([M +H]⁺) 92 ESIMS m/z 266.3 ([M + H]⁺) 93 ESIMS m/z 254.2 ([M + H]⁺) 94ESIMS m/z 254.2 ([M + H]⁺) 95 ESIMS m/z 236.2 ([M + H]⁺) 96 ESIMS m/z240.2 ([M + H]⁺) 97 ESIMS m/z 266.3 ([M + H]⁺) 98 ESIMS m/z 250.3 ([M +H]⁺) 99 ESIMS m/z 250.3 ([M + H]⁺) 100 ESIMS m/z 290.2 ([M + H]⁺) 101ESIMS m/z 308.1 ([M + H]⁺) 102 ESIMS m/z 214.2 ([M + H]⁺) 103 ESIMS m/z290.2 ([M + H]⁺) 104 ESIMS m/z 308.1 ([M + H]⁺) 105 ESIMS m/z 214.2([M + H]⁺) 106 ESIMS m/z 250.2 ([M + H]⁺) 107 ESIMS m/z 268.2 ([M + H]⁺)108 ESIMS m/z 250.2 ([M + H]⁺) 109 ESIMS m/z 268.2 ([M + H]⁺) 110 ESIMSm/z 250.2 ([M + H]⁺) 111 ESIMS m/z 268.2 ([M + H]⁺) 112 HRMS-ESI (m/z)[M + H]⁺ calcd for C₁₄H₂₂NO₃, 252.1600; found, 252.1443 113 HRMS-ESI(m/z) [M + H]⁺ calcd for C₁₃H₂₀NO₂, 222.1489; found, 222.1485 114 IR(thin film) 2854, 1740, 1233, 1203, 1118, 1078, 872, 796 cm⁻¹ 115HRMS-ESI (m/z) [M + H]⁺ calcd for C₁₄H₂₁FNO₃, 270.1500; found, 270.1501116 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.16(s, 1H), 8.52 (d, J = 7.8 Hz, 1H), C₂₂H₂₉N₂O₅, 8.00 (d, J = 5.2 Hz, 1H),7.09-7.03 (m, 401.2071; found, 1H), 7.00-6.94 (m, 2H), 6.88 (d, J = 5.1Hz, 401.2067 1H), 5.13 (dq, J = 8.4, 6.2 Hz, 1H), 4.79-4.67 (m, 1H),3.95 (s, 3H), 3.16 (dq, J = 8.9, 7.0 Hz, 1H), 2.31 (s, 3H), 2.28 (s,3H), 1.57 (d, J = 7.2 Hz, 3H), 1.24 (d, J = 6.9 Hz, 3H), 1.14 (d, J =6.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.86, 168.68, 155.38, 148.77,140.50, 138.63, 135.76, 135.33, 131.31, 130.52, 126.97, 126.26, 109.44,56.08, 48.18, 39.45, 20.89, 19.87, 18.48, 18.46, 17.56. 117 HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.17 (d, J = 0.6 Hz,1H), 8.50 (d, J = 7.9 Hz, C₂₂H₂₉N₂O₅, 1H), 8.01 (d, J = 5.2 Hz, 1H),401.2071; found, 7.10-7.02 (m, 1H), 6.97 (d, J = 6.9 Hz, 2H), 401.20646.88 (d, J = 5.2 Hz, 1H), 5.16 (dq, J = 8.4, 6.2 Hz, 1H), 4.77-4.68 (m,1H), 3.95 (s, 3H), 3.19-3.09 (m, 1H), 2.31 (s, 3H), 2.27 (s, 3H), 1.54(d, J = 7.2 Hz, 3H), 1.23 (d, J = 6.9 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H).¹³C NMR (126 MHz, CDCl₃) δ 171.87, 168.72, 155.38, 148.76, 140.50,138.60, 135.72, 135.36, 131.29, 130.53, 127.00, 126.28, 109.44, 56.08,47.99, 39.42, 20.87, 19.88, 18.31, 18.26, 17.65. 118 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.04 (s, 1H), 8.46 (t, J =5.8 Hz, 1H), C₂₀H₂₃FN₂O₅, 8.01 (d, J = 5.2 Hz, 1H), 7.18-7.06 (m,391.1664; found, 1H), 6.93-6.79 (m, 3H), 5.15 (dq, J = 8.0, 391.1662 6.3Hz, 1H), 4.21 (dd, J = 5.7, 3.2 Hz, 2H), 3.95 (s, 3H), 3.15 (p, J = 7.1Hz, 1H), 2.33 (s, 3H), 1.24 (d, J = 6.9 Hz, 3H), 1.15 (d, J = 6.3 Hz,3H). ¹³C NMR (126 MHz, CDCl₃) δ 169.32, 168.74, 161.97, 160.03, 155.39,148.70, 140.61, 137.91, 137.20, 130.40, 127.85, 117.11, 116.95, 113.07,112.90, 109.54, 76.40, 56.10, 41.03, 39.10, 20.00, 18.22, 17.42. 119HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.01 (s,1H), 8.34 (t, J = 5.8 Hz, 1H), C₂₀H₂₃FN₂O₅, 7.99 (d, J = 5.2 Hz, 1H),7.15 (dd, J = 9.5, 391.1664; found, 5.8 Hz, 1H), 6.88 (d, J = 5.2 Hz,1H), 391.1660 6.85-6.75 (m, 2H), 5.24-5.10 (m, 1H), 4.23-3.92 (m, 5H),3.23 (p, J = 7.1 Hz, 1H), 2.33 (s, 3H), 1.25 (m, 6H). ¹³C NMR (126 MHz,CDCl₃) δ 169.19, 168.38, 161.97, 160.02, 155.38, 148.68, 140.55, 138.37,136.63, 130.36, 127.68, 116.81, 116.65, 112.86, 112.70, 109.52, 75.82,56.09, 40.88, 38.65, 19.86, 17.20, 16.64. 120 HRMS-ESI (m/z) ¹H NMR (500MHz, CDCl₃) δ [M + H]⁺ calcd for 12.03 (s, 1H), 8.34 (t, J = 5.8 Hz,1H), C₂₀H₂₄N₂O₅, 7.99 (d, J = 5.2 Hz, 1H), 7.20 (dd, J = 7.6, 373.1758;found, 1.3 Hz, 1H), 7.16-7.06 (m, 3H), 373.1754 6.87 (d, J = 5.2 Hz,1H), 5.24-5.17 (m, 1H), 4.16-3.89 (m, 2H), 3.95 (s, 3H), 3.29 (p, J =7.1 Hz, 1H), 2.35 (s, 3H), 1.27 (m, 6H). ¹³C NMR (126 MHz, CDCl₃) δ169.15, 168.40, 155.35, 148.66, 140.97, 140.52, 136.10, 130.41, 130.27,126.30, 126.20, 126.14, 109.48, 75.92, 56.08, 40.85, 39.18, 19.79,17.18, 16.37. 121 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺calcd for 12.04 (s, 1H), 8.46 (t, J = 5.8 Hz, 1H), C₁₉H₂₁FN₂O₅, 8.01 (d,J = 5.2 Hz, 1H), 7.15 (dd, J = 8.6, 377.1507; found, 5.5 Hz, 2H),7.01-6.94 (m, 2H), 377.1504 6.89 (d, J = 5.2 Hz, 1H), 5.16-5.05 (m, 1H),4.21 (dd, J = 5.8, 2.1 Hz, 2H), 3.95 (s, 3H), 2.92 (p, J = 7.1 Hz, 1H),1.28 (d, J = 7.0 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz,CDCl₃) δ 169.33, 168.65, 162.66, 160.72, 155.40, 148.71, 140.61, 138.35,130.40, 129.27, 129.21, 115.36, 115.19, 109.55, 76.35, 56.10, 44.12,41.06, 17.83, 17.27. 122 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M +H]⁺ calcd for 12.06 (s, 1H), 8.47 (t, J = 5.8 Hz, 1H), C₂₁H₂₆N₂O₆, 8.01(d, J = 5.2 Hz, 1H), 7.08 (d, J = 8.4 Hz, 403.1864; found, 1H), 6.88 (d,J = 5.2 Hz, 1H), 403.1835 6.77-6.66 (m, 2H), 5.15 (dq, J = 8.2, 6.3 Hz,1H), 4.22 (dd, J = 5.7, 2.0 Hz, 2H), 3.95 (s, 3H), 3.77 (s, 3H),3.18-3.07 (m, 1H), 2.32 (s, 3H), 1.23 (d, J = 6.9 Hz, 3H), 1.14 (d, J =6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 169.30, 168.80, 157.71, 155.38,148.69, 140.60, 136.96, 133.70, 130.44, 127.36, 115.97, 111.49, 109.52,76.84, 56.09, 55.12, 41.05, 39.03, 20.17, 18.27, 17.59. 123 HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.04 (s, 1H), 8.46(t, J = 5.8 Hz, 1H), C₂₀H₂₃FN₂O₅, 8.00 (d, J = 5.2 Hz, 1H), 7.20-7.08(m, 391.1664; found, 1H), 6.93-6.80 (m, 3H), 5.15 (dq, J = 7.9, 391.16626.3 Hz, 1H), 4.21 (dd, J = 5.7, 3.2 Hz, 2H), 3.95 (s, 3H), 3.15 (p, J =7.1 Hz, 1H), 2.33 (s, 3H), 1.24 (d, J = 6.9 Hz, 3H), 1.15 (d, J = 6.3Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 169.32, 168.75, 161.97, 160.03,155.39, 148.70, 140.61, 137.91, 137.85, 137.20, 137.17, 130.40, 127.85,127.78, 117.11, 116.95, 113.06, 112.90, 109.54, 76.40, 56.10, 41.03,39.10, 19.99, 18.22, 17.42. 124 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ[M + H]⁺ calcd for 12.01 (d, J = 0.6 Hz, 1H), 8.34 (t, J = 5.8 Hz,C₂₀H₂₃FN₂O₅, 1H), 7.99 (d, J = 5.2 Hz, 1H), 7.15 (dd, 391.1664; found, J= 9.5, 5.8 Hz, 1H), 6.88 (d, J = 5.2 Hz, 391.1661 1H), 6.85-6.77 (m,2H), 5.21-5.11 (m, 1H), 4.20-3.91 (m, 2H), 3.95 (s, 3H), 3.23 (p, J =7.1 Hz, 1H), 2.33 (s, 3H), 1.30-1.20 (m, 6H). ¹³C NMR (126 MHz, CDCl₃) δ169.19, 168.38, 161.97, 160.02, 155.38, 148.68, 140.55, 138.43, 136.66,130.36, 127.75, 127.68, 116.81, 116.65, 112.86, 112.70, 109.52, 75.82,56.09, 40.88, 38.65, 19.85, 17.20, 16.64. 125 HRMS-ESI (m/z) ¹H NMR (500MHz, CDCl₃) δ [M + H]⁺ calcd for 12.03 (d, J = 0.6 Hz, 1H), 8.34 (t, J =5.8 Hz, C₂₀H₂₄N₂O₅, 1H), 7.99 (d, J = 5.2 Hz, 1H), 7.20 (dd, 373.1758;found, J = 7.7, 1.3 Hz, 1H), 7.17-7.04 (m, 373.1755 3H), 6.87 (d, J =5.2 Hz, 1H), 5.25-5.16 (m, 1H), 4.12 (dd, J = 18.2, 5.9 Hz, 1H), 3.95(s, 3H), 3.98-3.89 (m, 1H), 3.29 (p, J = 7.1 Hz, 1H), 2.35 (s, 3H), 1.27(m, 6H). ¹³C NMR (126 MHz, CDCl₃) δ 169.15, 168.41, 155.35, 148.66,140.97, 140.52, 136.10, 130.41, 130.27, 126.30, 126.14, 109.48, 75.92,56.08, 40.85, 39.18, 19.79, 17.18, 16.37. 126 HRMS-ESI (m/z) ¹H NMR (500MHz, CDCl₃) δ [M + H]⁺ calcd for 12.04 (s, 1H), 8.46 (t, J = 5.9 Hz,1H), C₁₉H₂₁FN₂O₅, 8.01 (d, J = 5.2 Hz, 1H), 7.22-7.08 (m, 377.1507;found, 2H), 6.98 (t, J = 8.7 Hz, 2H), 6.89 (d, J = 5.2 Hz, 377.1507 1H),5.16-5.01 (m, 1H), 4.29-4.14 (m, 2H), 3.95 (s, 3H), 2.92 (p, J = 7.1 Hz,1H), 1.28 (d, J = 7.0 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). ¹³C NMR (126MHz, CDCl₃) δ 169.33, 168.65, 162.67, 160.72, 155.41, 148.71, 140.61,138.37, 130.40, 129.27, 129.21, 115.36, 115.19, 109.55, 76.36, 56.10,44.12, 41.06, 17.83, 17.27. 127 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ[M + H]⁺ calcd for 12.06 (s, 1H), 8.47 (t, J = 5.7 Hz, 1H), C₂₁H₂₆N₂O₆,8.01 (d, J = 5.2 Hz, 1H), 7.08 (d, J = 8.4 Hz, 403.1864; found, 1H),6.88 (d, J = 5.2 Hz, 1H), 403.1853 6.82-6.66 (m, 2H), 5.15 (dq, J = 8.1,6.3 Hz, 1H), 4.29-4.15 (m, 2H), 3.95 (s, 3H), 3.77 (s, 3H), 3.17-3.08(m, 1H), 2.32 (s, 3H), 1.23 (d, J = 6.9 Hz, 3H), 1.14 (d, J = 6.3 Hz,3H). ¹³C NMR (126 MHz, CDCl₃) δ 169.30, 168.80, 157.71, 155.38, 148.69,140.60, 136.96, 133.70, 130.44, 127.36, 115.97, 111.49, 109.52, 76.84,56.09, 55.12, 41.05, 39.03, 20.17, 18.27, 17.59. 128 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.14 (d, J = 0.6 Hz, 1H),8.49 (d, J = 7.9 Hz, C₂₄H₂₅FN₂O₅, 1H), 8.00 (d, J = 5.2 Hz, 1H),405.1820; found, 7.18-7.05 (m, 1H), 6.93-6.79 (m, 3H), 405.1819 5.11(dq, J = 8.0, 6.3 Hz, 1H), 4.78-4.64 (m, 1H), 3.95 (s, 3H), 3.23-3.09(m, 1H), 2.33 (s, 3H), 1.55 (d, J = 7.2 Hz, 3H), 1.24 (d, J = 6.9 Hz,3H), 1.14 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.79,168.69, 161.97, 160.03, 155.39, 148.77, 140.51, 137.87, 137.81, 137.33,137.30, 130.47, 127.86, 127.79, 117.10, 116.94, 113.02, 112.85, 109.47,76.32, 56.09, 48.13, 39.16, 20.00, 18.42, 18.36, 17.33. 129 HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.09 (s, 1H), 8.35(d, J = 7.9 Hz, 1H), C₂₁H₂₅FN₂O₅, 7.98 (dd, J = 5.2, 3.6 Hz, 1H), 7.13(dd, J = 8.4, 405.1820; found, 5.8 Hz, 1H), 6.94-6.73 (m, 3H), 405.18205.21-5.08 (m, 1H), 4.63-4.46 (m, 1H), 3.94 (s, 2H), 3.27-3.15 (m, 1H).¹³C NMR (126 MHz, CDCl₃) δ 171.55, 168.59, 161.91, 159.97, 155.37,148.73, 140.44, 138.30, 137.15, 130.43, 127.47, 116.73, 116.57, 112.89,112.73, 109.43, 75.74, 56.07, 47.87, 38.98, 19.90, 17.79, 17.32. 130HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.11 (s,1H), 8.36 (d, J = 8.0 Hz, 1H), C₂₁H₂₆N₂O₅, 7.97 (d, J = 5.2 Hz, 1H),7.24-7.01 (m, 387.1914; found, 4H), 6.86 (d, J = 5.2 Hz, 1H), 387.19115.27-5.12 (m, 1H), 4.59-4.47 (m, 1H), 3.94 (s, 2H), 3.33-3.20 (m, 1H),2.36 (s, 3H), 1.32 (d, J = 6.3 Hz, 3H), 1.24 (d, J = 7.1 Hz, 3H), 1.08(d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.58, 168.54, 155.33,148.71, 141.47, 140.41, 135.95, 130.49, 130.22, 126.20, 125.88, 109.39,75.87, 56.06, 47.85, 39.52, 19.83, 17.83, 17.74, 17.14. 131 HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.14 (s, 1H), 8.47(d, J = 8.0 Hz, 1H), C₂₀H₂₃FN₂O₅, 8.00 (d, J = 5.2 Hz, 1H), 7.15 (dd, J= 8.6, 391.1664; found, 5.4 Hz, 2H), 6.97 (t, J = 8.7 Hz, 2H), 391.16626.88 (d, J = 5.2 Hz, 1H), 5.11-5.02 (m, 1H), 4.71 (p, J = 7.3 Hz, 1H),3.95 (s, 3H), 2.92 (p, J = 7.1 Hz, 1H), 1.53 (d, J = 7.2 Hz, 3H), 1.29(d, J = 7.1 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃)δ 171.67, 168.69, 162.64, 160.70, 155.40, 148.78, 140.51, 138.48,130.46, 129.26, 129.19, 115.32, 115.16, 109.48, 76.31, 56.09, 48.12,44.11, 18.38, 17.95, 17.16. 132 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ[M + H]⁺ calcd for 12.16 (s, 1H), 8.51 (d, J = 7.9 Hz, 1H), C₂₂H₂₈N₂O₆,8.00 (d, J = 5.2 Hz, 1H), 7.11-7.05 (m, 417.2020; found, 1H), 6.88 (d, J= 5.2 Hz, 1H), 6.70 (d, J = 6.7 Hz, 417.2007 2H), 5.11 (dq, J = 8.3, 6.3Hz, 1H), 4.72 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H), 3.77 (s, 3H), 3.18-3.06(m, 1H), 2.32 (s, 3H), 1.56 (d, J = 7.2 Hz, 3H), 1.23 (d, J = 6.9 Hz,3H), 1.14 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.85,168.67, 157.70, 155.38, 148.77, 140.50, 136.91, 133.86, 130.52, 127.36,115.95, 111.48, 109.45, 56.08, 55.13, 48.17, 39.11, 20.18, 18.46, 17.57,16.10. 133 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for12.14 (s, 1H), 8.47 (d, J = 8.0 Hz, 1H), C₂₄H₂₅FN₂O₅, 8.01 (d, J = 5.2Hz, 1H), 7.13 (dd, J = 9.4, 405.1820; found, 5.8 Hz, 1H), 6.91-6.81 (m,3H), 405.1819 5.12 (dq, J = 8.1, 6.3 Hz, 1H), 4.72 (p, J = 7.2 Hz, 1H),3.95 (s, 3H), 3.20-3.10 (m, 1H), 2.33 (s, 3H), 1.54 (d, J = 7.1 Hz, 3H),1.23 (d, J = 6.9 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz,CDCl₃) δ 171.81, 168.74, 161.95, 160.01, 155.40, 148.78, 140.51, 137.89,137.83, 137.29, 137.26, 130.48, 127.87, 127.81, 117.08, 116.91, 113.06,112.90, 109.48, 76.19, 56.09, 47.96, 39.12, 20.02, 18.24, 18.12, 17.47.134 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.12(s, 1H), 8.28 (d, J = 8.0 Hz, 1H), C₂₄H₂₅FN₂O₅, 7.99 (d, J = 5.2 Hz,1H), 7.18-7.12 (m, 405.1820; found, 1H), 6.88 (d, J = 5.2 Hz, 1H), 6.78(t, J = 8.2 Hz, 405.1818 2H), 5.17-5.06 (m, 1H), 4.64-4.51 (m, 1H), 3.95(s, 3H), 3.23 (p, J = 7.1 Hz, 1H), 2.33 (s, 3H), 1.38 (d, J = 7.1 Hz,3H), 1.26-1.20 (m, 6H). ¹³C NMR (126 MHz, CDCl₃) δ 171.29, 168.55,161.93, 159.99, 155.38, 148.74, 140.44, 138.41, 138.35, 136.73, 136.71,130.43, 127.71, 127.65, 116.77, 116.61, 112.81, 112.64, 109.45, 75.62,56.09, 47.82, 38.64, 19.89, 19.88, 18.06, 17.22, 16.84. 135 HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.15 (s, 1H), 8.30(d, J = 8.0 Hz, 1H), C₂₁H₂₆N₂O₅, 7.99 (d, J = 5.2 Hz, 1H), 7.21 (dd, J =7.8, 387.1914; found, 1.4 Hz, 1H), 7.15-7.00 (m, 3H), 387.1915 6.87 (d,J = 5.2 Hz, 1H), 5.20-5.12 (m, 1H), 4.59-4.50 (m, 1H), 3.95 (s, 3H),3.29 (p, J = 7.1 Hz, 1H), 2.36 (s, 3H), 1.35 (d, J = 7.2 Hz, 3H),1.29-1.22 (m, 6H). ¹³C NMR (126 MHz, CDCl₃) δ 171.30, 168.54, 155.35,148.73, 141.04, 140.40, 136.09, 130.51, 130.26, 126.23, 126.11, 109.40,75.73, 56.08, 47.88, 39.15, 19.83, 18.11, 17.16, 16.53. 136 HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.14 (s, 1H), 8.46(d, J = 7.7 Hz, 1H), C₂₀H₂₃FN₂O₅, 8.00 (dd, J = 5.2, 2.2 Hz, 1H), 7.15(ddd, J = 9.9, 391.1664; found, 6.1, 3.4 Hz, 2H), 6.97 (td, J = 8.8,391.1658 2.6 Hz, 2H), 6.88 (dd, J = 5.4, 1.5 Hz, 1H), 5.12-5.01 (m, 1H),4.77-4.64 (m, 1H), 3.95 (s, 3H), 2.92 (p, J = 7.1 Hz, 1H), 1.53 (d, J =7.2 Hz, 3H), 1.28 (d, J = 7.0 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H). ¹³C NMR(126 MHz, CDCl₃) δ 171.72, 168.76, 162.65, 160.70, 155.41, 148.78,140.51, 138.43, 138.40, 130.47, 129.29, 129.23, 115.33, 115.16, 109.48,76.12, 56.09, 47.98, 44.09, 18.20, 17.69, 17.30. 137 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.17 (s, 1H), 8.50 (d, J =7.9 Hz, 1H), C₂₂H₂₈N₂O₆, 8.01 (d, J = 5.2 Hz, 1H), 7.09 (d, J = 8.4 Hz,417.2020; found, 1H), 6.88 (d, J = 5.2 Hz, 1H), 417.2010 6.76-6.67 (m,2H), 5.13 (dq, J = 8.3, 6.3 Hz, 1H), 4.72 (p, J = 7.3 Hz, 1H), 3.95 (s,3H), 3.76 (s, 3H), 3.18-3.07 (m, 1H), 2.32 (s, 3H), 1.54 (d, J = 7.2 Hz,3H), 1.23 (d, J = 6.9 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). ¹³C NMR (126MHz, CDCl₃) δ 171.86, 168.72, 157.68, 155.38, 148.76, 140.50, 136.94,133.82, 130.53, 127.37, 115.97, 111.47, 109.45, 76.65, 56.08, 55.11,47.99, 39.06, 20.19, 18.31, 18.20, 17.68. 138 HRMS-ESI (m/z) ¹H NMR (500MHz, CDCl₃) δ [M + H]⁺ calcd for 12.16 (s, 1H), 8.50 (d, J = 9.4 Hz,1H), C₂₃H₂₉FN₂O_(5,) 8.01 (d, J = 5.2 Hz, 1H), 7.11 (dd, J = 8.6,433.2133; found, 5.8 Hz, 1H), 6.89 (d, J = 5.2 Hz, 1H), 433.21306.87-6.77 (m, 2H), 5.08 (dq, J = 8.0, 6.2 Hz, 1H), 4.65 (dd, J = 9.4,4.8 Hz, 1H), 3.95 (s, 3H), 3.15 (p, J = 7.1 Hz, 1H), 2.32 (s, 4H), 1.24(d, J = 6.9 Hz, 3H), 1.14 (d, J = 6.2 Hz, 3H), 1.05 (d, J = 6.8 Hz, 3H),0.96 (d, J = 6.8 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 170.73, 169.06,161.95, 160.01, 155.42, 148.75, 140.52, 137.83, 137.77, 137.36, 130.51,127.84, 127.78, 117.07, 116.91, 113.01, 112.85, 109.47, 76.43, 57.26,56.09, 39.06, 31.35, 19.99, 19.48, 18.45, 17.38. 139 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.12 (s, 1H), 8.38 (d, J =9.3 Hz, 1H), C₂₃H₂₉FN₂O₅, 7.99 (t, J = 5.1 Hz, 1H), 7.14 (dd, J = 8.5,433.2133; found, 5.9 Hz, 1H), 6.88 (dd, J = 7.6, 5.1 Hz, 433.213 1H),6.84-6.72 (m, 3H), 5.13 (dq, J = 8.4, 6.3 Hz, 1H), 4.49 (td, J = 9.4,4.9 Hz, 1H), 3.94 (s, 3H), 3.20 (p, J = 7.4 Hz, 1H), 2.33 (s, 3H), 1.94(pd, J = 6.9, 4.6 Hz, 1H), 1.29 (d, J = 6.3 Hz, 3H), 1.21 (d, J = 7.1Hz, 3H), 0.85 (d, J = 6.9 Hz, 3H), 0.68 (d, J = 6.8 Hz, 3H). ¹³C NMR(126 MHz, CDCl₃) δ 170.52, 168.98, 161.96, 160.02, 155.39, 148.70,140.45, 138.31, 138.25, 137.28, 137.25, 130.49, 127.46, 127.40, 116.75,116.59, 112.92, 112.76, 109.42, 75.86, 56.97, 56.08, 38.86, 31.12,19.89, 19.12, 17.79, 17.34, 17.02. 140 HRMS-ESI (m/z) ¹H NMR (500 MHz,CDCl₃) δ 8.38 (d, [M + H]⁺ calcd for J = 9.4 Hz, 1H), 7.99 (d, J = 5.2Hz, C₂₃H₃₀N₂O₅, 1H), 7.20 (d, J = 7.7 Hz, 1H), 415.2227; found,7.16-7.08 (m, 1H), 7.08-7.03 (m, 2H), 415.2222 6.86 (d, J = 5.2 Hz, 1H),5.25-5.11 (m, 1H), 4.49 (dd, J = 9.4, 4.5 Hz, 1H), 3.94 (s, 3H),3.37-3.18 (m, 1H), 2.34 (s, 3H), 1.91 (pd, J = 6.9, 4.5 Hz, 1H), 1.31(d, J = 6.2 Hz, 3H), 1.23 (d, J = 7.1 Hz, 3H), 0.82 (d, J = 6.8 Hz, 3H),0.64 (d, J = 6.8 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 170.54, 168.94,155.34, 148.67, 141.56, 140.42, 135.94, 130.56, 130.25, 126.23, 125.89,109.37, 75.96, 56.90, 56.07, 39.37, 31.11, 19.82, 19.14, 17.78, 17.11,16.98. 141 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for12.16 (s, 1H), 8.48 (d, J = 9.4 Hz, 1H), C₂₂H₂₇FN₂O₅, 8.01 (d, J = 5.2Hz, 1H), 7.19-7.10 (m, 419.1977; found, 2H), 6.94 (t, J = 8.7 Hz, 2H),6.89 (d, J = 5.2 Hz, 419.1973 1H), 5.11-4.98 (m, 1H), 4.64 (dd, J = 9.4,4.8 Hz, 1H), 3.95 (s, 3H), 2.92 (p, J = 7.1 Hz, 1H), 2.31 (pd, J = 6.9,4.8 Hz, 1H), 1.29 (d, J = 7.0 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H), 1.03(d, J = 6.8 Hz, 3H), 0.95 (d, J = 6.9 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃)δ 170.57, 169.05, 162.62, 160.67, 155.43, 148.76, 140.52, 138.50,130.50, 129.23, 129.16, 115.29, 115.13, 109.47, 77.27, 76.39, 57.25,56.10, 43.96, 31.33, 19.41, 18.04, 17.40, 17.07. 142 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.18 (s, 1H), 8.52 (d, J =9.4 Hz, 1H), C₂₄H₃₂N₂O₆, 8.02 (d, J = 5.2 Hz, 1H), 7.06 (d, J = 8.4 Hz,445.2333; found, 1H), 6.88 (d, J = 5.2 Hz, 1H), 445.2314 6.75-6.63 (m,2H), 5.08 (dq, J = 8.3, 6.2 Hz, 1H), 4.66 (dd, J = 9.4, 4.8 Hz, 1H),3.95 (s, 3H), 3.76 (s, 3H), 3.19-3.06 (m, 1H), 2.41-2.33 (m, 1H), 2.31(s, 3H), 1.23 (d, J = 6.9 Hz, 3H), 1.13 (d, J = 6.2 Hz, 3H), 1.05 (d, J= 6.9 Hz, 3H), 0.98 (d, J = 6.9 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ170.79, 169.06, 157.68, 155.40, 148.74, 140.51, 136.87, 133.93, 130.56,127.33, 115.96, 111.46, 109.44, 76.90, 57.29, 56.08, 55.12, 39.01,31.37, 20.17, 19.50, 18.52, 17.65, 17.40. 143 HRMS-ESI (m/z) ¹H NMR (500MHz, CDCl₃) δ [M + H]⁺ calcd for 12.18 (s, 1H), 8.50 (d, J = 9.2 Hz,1H), C₂₃H₂₉FN₂O₅, 8.02 (d, J = 5.2 Hz, 1H), 7.13 (dd, J = 9.5, 433.2133;found, 5.7 Hz, 1H), 6.89 (d, J = 5.2 Hz, 1H), 433.2142 6.87-6.82 (m,2H), 5.12 (dq, J = 8.0, 6.3 Hz, 1H), 4.63 (dd, J = 9.3, 5.1 Hz, 1H),3.95 (s, 3H), 3.15 (p, J = 7.1 Hz, 1H), 2.41-2.25 (m, 4H), 1.24 (d, J =6.9 Hz, 3H), 1.13 (d, J = 6.3 Hz, 3H), 1.03 (d, J = 6.9 Hz, 3H), 0.99(d, J = 6.9 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 170.87, 169.06, 161.95,160.01, 155.41, 148.74, 140.53, 137.86, 137.80, 137.31, 137.28, 130.54,127.91, 117.05, 116.89, 113.06, 112.89, 109.46, 76.09, 57.04, 56.09,39.11, 31.39, 20.00, 19.12, 18.25, 17.80, 17.41. 144 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.16 (s, 1H), 8.32 (d, J =9.2 Hz, 1H), C₂₃H₂₉FN₂O₅, 8.00 (d, J = 5.2 Hz, 1H), 7.16 (dd, J = 8.4,433.2133; found, 5.8 Hz, 1H), 6.89 (d, J = 5.2 Hz, 1H), 433.2139 6.78(ddd, J = 9.8, 7.0, 4.1 Hz, 2H), 5.17-5.05 (m, 1H), 4.48 (dd, J = 9.3,5.3 Hz, 1H), 3.96 (s, 3H), 3.22 (p, J = 7.2 Hz, 1H), 2.33 (s, 3H), 2.18(pd, J = 6.9, 5.2 Hz, 1H), 1.28-1.19 (m, 6H), 0.92 (d, J = 6.8 Hz, 3H),0.86 (d, J = 6.9 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 170.29, 168.86,161.96, 160.02, 155.40, 148.71, 140.46, 138.45, 138.39, 136.79, 136.76,130.49, 127.77, 127.70, 116.77, 116.61, 112.79, 112.63, 109.43, 75.66,57.06, 56.09, 38.58, 31.26, 19.91, 18.94, 17.61, 17.30, 16.84. 145HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.19 (s,1H), 8.34 (d, J = 9.3 Hz, 1H), C₂₃H₃₀N₂O₅, 8.00 (d, J = 5.2 Hz, 1H),7.21 (dd, J = 7.6, 415.2227; found, 1.7 Hz, 1H), 7.14-7.05 (m, 2H),415.2224 7.02 (td, J = 7.2, 1.4 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1H),5.20-5.12 (m, 1H), 4.48 (dd, J = 9.3, 5.1 Hz, 1H), 3.95 (s, 3H), 3.28(p, J = 7.1 Hz, 1H), 2.36 (s, 3H), 2.17 (pd, J = 6.9, 5.1 Hz, 1H),1.29-1.22 (m, 6H), 0.90 (d, J = 6.8 Hz, 3H), 0.84 (d, J = 6.8 Hz, 3H).¹³C NMR (126 MHz, CDCl₃) δ 170.28, 168.84, 155.36, 148.69, 141.08,140.42, 136.11, 130.59, 130.28, 126.23, 126.11, 109.39, 75.76, 57.06,56.08, 39.06, 31.33, 19.83, 18.93, 17.59, 17.20, 16.50. 146 HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.17 (s, 1H), 8.50(d, J = 8.9 Hz, 1H), C₂₂H₂₇FN₂O₅, 8.02 (d, J = 5.2 Hz, 1H), 7.19-7.10(m, 419.1977; found, 3H), 7.00-6.93 (m, 2H), 6.89 (d, J = 5.2 Hz,419.1974 1H), 5.11-5.02 (m, 1H), 4.67-4.58 (m, 1H), 3.95 (s, 4H), 2.92(p, J = 7.1 Hz, 1H), 2.31 (pd, J = 6.9, 5.0 Hz, 1H), 1.28 (d, J = 7.0Hz, 3H), 1.10 (d, J = 6.2 Hz, 3H), 1.02 (d, J = 6.9 Hz, 3H), 0.99 (d, J= 6.9 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 170.76, 169.06, 162.64,160.70, 155.41, 148.74, 140.53, 138.48, 130.53, 129.28, 129.22, 115.33,115.16, 109.46, 76.11, 57.07, 56.09, 44.09, 31.35, 19.09, 17.87, 17.82,17.23. 147 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for12.20 (s, 1H), 8.53 (d, J = 9.2 Hz, 1H), C₂₄H₃₂N₂O₆, 8.02 (d, J = 5.2Hz, 1H), 7.10 (d, J = 8.4 Hz, 445.2333; found, 1H), 6.88 (d, J = 5.2 Hz,1H), 445.2334 6.75-6.64 (m, 2H), 5.12 (dq, J = 8.2, 6.3 Hz, 1H), 4.65(dd, J = 9.2, 5.0 Hz, 1H), 3.95 (s, 3H), 3.75 (s, 3H), 3.20-3.06 (m,1H), 2.32 (s, 4H), 1.23 (d, J = 6.9 Hz, 3H), 1.13 (d, J = 6.2 Hz, 3H),1.03 (d J = 6.9 Hz, 3H), 1.00 (d, J = 6.9 Hz, 3H). ¹³C NMR (126 MHz,CDCl₃) δ 170.92, 169.04, 157.67, 155.39, 148.73, 140.52, 136.92, 133.85,130.59, 127.40, 116.00, 111.44, 109.43, 76.56, 57.04, 56.08, 55.10,39.05, 31.44, 20.18, 19.13, 18.32, 17.80, 17.65. 148 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.14 (s, 1H), 8.47 (d, J =7.9 Hz, 1H), C₂₁H₂₅FN₂O₅, 8.01 (d, J = 5.2 Hz, 1H), 7.13 (dd, J = 9.5,405.1820; found, 5.8 Hz, 1H), 6.91-6.80 (m, 3H), 405.1820 5.12 (dq, J =8.1, 6.3 Hz, 1H), 4.72 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H), 3.21-3.10 (m,1H), 2.33 (s, 3H), 1.54 (d, J = 7.2 Hz, 3H), 1.23 (d, J = 6.9 Hz, 3H),1.12 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.81, 168.74,161.95, 160.01, 155.40, 148.78, 140.51, 137.89, 137.83, 137.29, 137.26,130.48, 127.87, 127.81, 117.07, 116.91, 113.06, 112.90, 109.48, 76.19,56.09, 47.96, 39.12, 20.01, 18.24, 18.13, 17.48. 149 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.12 (s, 1H), 8.28 (d, J =8.0 Hz, 1H), C₂₁H₂₅FN₂O₅, 7.99 (d, J = 5.2 Hz, 1H), 7.22-7.09 (m,405.1820; found, 1H), 6.88 (d, J = 5.2 Hz, 1H), 405.1820 6.83-6.74 (m,2H), 5.19-5.06 (m, 1H), 4.62-4.50 (m, 1H), 3.95 (s, 3H), 3.31-3.17 (m,1H) 2.33 (s, 3H) 1.38 (d, J = 7.2 Hz, 3H), 1.27-1.18 (m, 6H). ¹³C NMR(126 MHz, CDCl₃) δ 171.29, 168.55, 161.93, 159.99, 155.38, 148.74,140.44, 138.41, 138.35, 136.73, 136.71, 130.43, 127.71, 127.64, 116.77,116.61, 112.80, 112.64, 109.45, 75.62, 56.09, 47.82, 38.64, 18.06,17.22, 16.84. 150 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺calcd for 12.15 (s, 1H), 8.30 (d, J = 7.9 Hz, 1H), C₂₁H₂₆N₂O₅, 7.99 (d,J = 5.2 Hz, 1H), 7.21 (dd, J = 7.8, 387.1914; found, 1.4 Hz, 1H),7.15-7.01 (m, 4H), 387.1913 6.87 (d, J = 5.2 Hz, 1H), 5.23-5.08 (m, 1H),4.58-4.49 (m, 1H), 3.95 (s, 3H), 3.28 (h, J = 7.3 Hz, 1H), 2.36 (s, 3H),1.35 (d, J = 7.2 Hz, 3H), 1.28-1.22 (m, 6H). ¹³C NMR (126 MHz, CDCl₃) δ171.29, 168.54, 155.35, 148.73, 141.04, 140.40, 136.09, 130.51, 130.26,126.23, 126.11, 109.40, 75.73, 56.08, 47.88, 39.15, 19.83, 18.11, 17.16,16.53. 151 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for12.14 (d, J = 0.6 Hz, 1H), 8.46 (d, J = 7.9 Hz, C₂₀H₂₃FN₂O₅, 1H), 8.01(d, J = 5.2 Hz, 1H), 7.16 (dd, 391.1664; found, J = 8.7, 5.4 Hz, 2H),6.97 (t, J = 8.7 Hz, 391.1658 2H), 6.88 (d, J = 5.2 Hz, 1H), 5.07 (dq, J= 7.4, 6.3 Hz, 1H), 4.79-4.64 (m, 1H), 3.95 (s, 3H), 2.92 (p, J = 7.1Hz, 1H), 1.53 (d, J = 7.2 Hz, 3H), 1.28 (d, J = 7.1 Hz, 3H), 1.09 (d, J= 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.72, 168.76, 162.65,160.70, 155.40, 148.78, 140.51, 138.43, 130.47, 129.29, 129.23, 115.33,115.16, 109.48, 76.12, 56.09, 47.98, 44.09, 18.19, 17.69, 17.30. 152HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.17 (s,1H), 8.50 (d, J = 7.9 Hz, 1H), C₂₂H₂₈N₂O₆, 8.01 (d, J = 5.2 Hz, 1H),7.09 (d, J = 8.3 Hz, 417.2020; found, 1H), 6.88 (d, J = 5.2 Hz, 1H),417.2007 6.78-6.64 (m, 2H), 5.13 (dq, J = 8.4, 6.3 Hz, 1H), 4.73 (p, J =7.3 Hz, 1H), 3.95 (s, 3H), 3.76 (s, 3H), 3.18-3.06 (m, 1H), 2.32 (s,3H), 1.54 (d, J = 7.2 Hz, 3H), 1.23 (d, J = 6.9 Hz, 3H), 1.12 (d, J =6.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.86, 168.72, 157.68, 155.38,148.76, 140.50, 136.94, 133.81, 130.53, 127.37, 115.97, 111.47, 109.45,76.65, 56.08, 55.11, 47.99, 39.06, 20.19, 18.30, 18.19, 17.68. 153HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.14 (s,1H), 8.49 (d, J = 8.0 Hz, 1H), C₂₁H₂₅FN₂O₅, 8.00 (d, J = 5.2 Hz, 1H),7.17-7.08 (m, 405.1820; found, 1H), 6.91-6.81 (m, 4H), 5.11 (dq, J =8.1, 405.1818 6.3 Hz, 1H), 4.72 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H),3.20-3.10 (m, 1H), 2.33 (s, 3H), 1.55 (d, J = 7.2 Hz, 3H), 1.24 (d, J =6.9 Hz, 3H), 1.14 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ171.80, 168.69, 161.97, 160.03, 155.39, 148.77, 140.51, 137.87, 137.81,137.33, 137.30, 130.47, 127.86, 127.79, 117.10, 116.94, 113.02, 112.86,109.47, 76.33, 56.09, 48.13, 39.16, 20.00, 18.41, 18.36, 17.33. 154HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.09 (s,1H), 8.35 (d, J = 8.0 Hz, 1H), C₂₁H₂₅FN₂O₅, 7.98 (d, J = 5.2 Hz, 1H),7.13 (dd, J = 8.4, 405.1820; found, 5.8 Hz, 1H), 6.86 (d, J = 5.2 Hz,1H), 405.1816 6.80 (ddd, J = 9.5, 7.0, 4.1 Hz, 2H), 5.14 (dq, J = 8.2,6.2 Hz, 1H), 4.60-4.49 (m, 1H), 3.94 (s, 3H), 3.27-3.16 (m, 1H), 2.34(s, 3H), 1.30 (d, J = 6.3 Hz, 3H), 1.22 (d, J = 7.1 Hz, 3H), 1.14 (d, J= 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.55, 168.59, 161.91,159.97, 155.37, 148.74, 140.44, 138.30, 138.24, 137.15, 137.13, 130.43,127.46, 127.40, 116.74, 116.57, 112.90, 112.73, 109.43, 75.74, 56.08,47.87, 38.98, 19.90, 19.89, 17.79, 17.32. 155 HRMS-ESI (m/z) ¹H NMR (500MHz, CDCl₃) δ [M + H]⁺ calcd for 12.11 (d, J = 0.6 Hz, 1H), 8.36 (d, J =8.0 Hz, C₂₁H₂₆N₂O₅, 1H), 7.97 (d, J = 5.2 Hz, 1H), 7.19 (dd, 387.1914;found, J = 7.5, 1.2 Hz, 1H), 7.12 (td, J = 7.8, 387.1912 7.0, 2.4 Hz,1H), 7.09-7.02 (m, 2H), 6.86 (d, J = 5.2 Hz, 1H), 5.19 (dq, J = 8.3, 6.2Hz, 1H), 4.60-4.45 (m, 1H), 3.94 (s, 3H), 3.33-3.20 (m, 1H), 2.36 (s,3H), 1.32 (d, J = 6.2 Hz, 3H), 1.24 (d, J = 7.0 Hz, 3H), 1.08 (d, J =7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.58, 168.54, 155.33, 148.71,141.47, 140.41, 135.95, 130.49, 130.22, 126.20, 125.88, 109.39, 75.87,56.06, 47.85, 39.52, 19.83, 17.83, 17.74, 17.14. 156 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.14 (s, 1H), 8.47 (d, J =7.7 Hz, 1H), C₂₀H₂₃FN₂O₅, 8.00 (d, J = 5.2 Hz, 1H), 7.21-7.10 (m,391.1664; found, 3H), 6.97 (td, J = 8.8, 2.6 Hz, 2H), 391.1661 6.88 (dd,J = 5.3, 1.7 Hz, 1H), 5.12-5.01 (m, 1H), 4.77-4.66 (m, 1H), 3.95 (d, J =1.6 Hz, 4H), 2.92 (p, J = 7.1 Hz, 1H), 1.53 (d, J = 7.2 Hz, 4H), 1.29(d, J = 7.0 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃)δ 171.67, 168.69, 162.64, 160.70, 155.40, 148.78, 140.51, 138.45,130.46, 129.26, 115.32, 115.16, 109.48, 76.31, 56.09, 48.12, 44.11,18.38, 17.95, 17.16. 157 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M +H]⁺ calcd for 12.16 (s, 1H), 8.51 (d, J = 7.9 Hz, 1H), C₂₂H₂₈N₂O₆, 8.00(d, J = 5.2 Hz, 1H), 7.12-7.06 (m, 417.2020; found, 1H), 6.88 (d, J =5.2 Hz, 1H), 417.2006 6.76-6.67 (m, 2H), 5.11 (dq, J = 8.3, 6.3 Hz, 1H),4.72 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H), 3.77 (s, 3H), 3.19-3.07 (m, 1H),2.32 (s, 3H), 1.61-1.51 (m, 4H), 1.23 (d, J = 6.9 Hz, 3H), 1.14 (d, J =6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.86, 168.68, 157.70, 155.38,148.77, 140.50, 136.91, 133.86, 130.51, 127.36, 115.95, 111.48, 109.45,56.08, 55.13, 48.17, 39.11, 20.18, 18.46, 17.57. 158 IR (thin HRMS-ESI(m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 3369, [M + H]⁺ calcd for 12.13 (s,1H), 8.58-8.47 (m, 1H), 8.01 (d, J = 5.2 Hz, 2983, 1736, C₂₁H₂₄F₃N₂O₅,1H), 7.68-7.61 (m, 1H), 1649, 1528, 441.1632; found, 7.51 (td, J = 7.7,1.2 Hz, 1H), 7.43 (d, J = 7.7 Hz, 1310, 1148, 441.1627 1H), 7.38-7.29(m, 1H), 1115, 770, 6.88 (d, J = 5.2 Hz, 1H), 731 cm⁻¹ 5.29-5.15 (m,1H), 4.82-4.71 (m, 1H), 3.95 (s, 3H), 3.42-3.29 (m, 1H), 1.60 (d, J =7.2 Hz, 3H), 1.29 (d, J = 6.8 Hz, 3H), 1.12 (d, J = 6.2 Hz, 3H). ¹⁹F NMR(376 MHz, CDCl₃) δ −58.24. 159 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz,CDCl₃) δ film) 3370, [M + H]⁺ calcd for 12.11 (s, 1H), 8.50 (d, J = 7.9Hz, 1H), 2984, 1737, C₂₁H₂₃F₄N₂O₅, 8.01 (d, J = 5.2 Hz, 1H), 7.42 (dd, J= 8.8, 1528, 1313, 459.1538; found, 5.3 Hz, 1H), 7.35 (dd, J = 9.2, 2.8Hz, 1151, 1118, 459.1535 1H), 7.21 (td, J = 8.2, 2.8 Hz, 1H), 1045, 908,6.89 (d, J = 5.2 Hz, 1H), 5.24-5.09 (m, 799, 738 cm⁻¹ 1H), 4.82-4.67 (m,1H), 3.95 (s, 3H), 3.41-3.26 (m, 1H), 1.59 (d, J = 7.2 Hz, 3H), 1.27 (d,J = 6.8 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ−58.78, −113.91. 160 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δfilm) 3369, [M + H]⁺ calcd for 12.17 (s, 1H), 8.53 (d, J = 7.8 Hz, 1H),2944, 1732, C₁₉H₂₉N₂O₅, 7.99 (d, J = 5.2 Hz, 1H), 6.87 (d, J = 5.2 Hz,1648, 1526, 365.2071; found, 1H), 5.11 (qd, J = 6.4, 3.1 Hz, 1H), 1438,1280, 365.2067 4.76-4.64 (m, 1H), 3.95 (s, 3H), 1263, 1216, 1.76 (dddd,J = 13.2, 10.4, 8.0, 6.4 Hz, 2H), 1149, 1057, 1.69-1.52 (m, 6H),1.52-1.43 (m, 800 cm⁻¹ 1H), 1.43-1.35 (m, 1H), 1.24 (d, J = 6.4 Hz, 3H),1.19-0.98 (m, 3H), 0.98-0.89 (m, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.76,168.71, 155.39, 148.78, 140.46, 130.58, 109.43, 74.81, 56.08, 48.23,43.31, 43.13, 31.22, 30.74, 25.15, 24.98, 18.51, 17.78, 12.50. 161HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ [M + H]⁺ calcd for 12.15 (s,1H), 8.48 (d, J = 8.0 Hz, 1H), C₂₁H₂₄F₃N₂O₅, 8.01 (d, J = 5.2 Hz, 1H),7.64 (dd, J = 7.9, 441.1632; found, 1.3 Hz, 1H), 7.56-7.47 (m, 1H),441.1624 7.44 (d, J = 7.8 Hz, 1H), 7.31 (t, J = 7.5 Hz, 1H), 6.88 (d, J= 5.2 Hz, 1H), 5.27-5.17 (m, 1H), 4.83-4.68 (m, 1H), 3.95 (s, 3H),3.42-3.28 (m, 1H), 1.58 (d, J = 7.2 Hz, 3H), 1.30 (d, J = 6.8 Hz, 3H),1.10 (d, J = 6.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.24. 162 IR(thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 2983, [M + H]⁺calcd for 12.12 (s, 1H), 8.46 (d, J = 7.9 Hz, 1H), 1738, 1649,C₂₁H₂₃F₄N₂O₅, 8.01 (d, J = 5.2 Hz, 1H), 7.43 (dd, J = 8.8, 1528, 1313,459.1538; found, 5.3 Hz, 1H), 7.34 (dd, J = 9.2, 2.8 Hz, 1152, 1119,459.1530 1H), 7.21 (td, J = 8.2, 2.8 Hz, 1H), 1045, 909, 6.89 (d, J =5.2 Hz, 1H), 5.18 (p, J = 6.6 Hz, 800, 732 cm⁻¹ 1H), 4.79-4.69 (m, 1H),3.95 (s, 3H), 3.31 (p, J = 7.1 Hz, 1H), 1.57 (d, J = 7.2 Hz, 3H), 1.29(d, J = 6.9 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃)δ −58.78, −114.01. 163 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δfilm) 3370, [M + H]⁺ calcd for 12.18 (s, 1H), 8.52 (d, J = 7.8 Hz, 1H),2944, 1732, C₁₉H₂₉N₂O₅, 7.99 (d, J = 5.2 Hz, 1H), 6.87 (d, J = 5.2 Hz,1649, 1526, 365.2071; found, 1H), 5.10 (qd, J = 6.4, 3.0 Hz, 1H), 1438,1263, 365.2068 4.74-4.64 (m, 1H), 3.95 (s, 3H), 1216, 1150, 1.83-1.65(m, 3H), 1.65-1.52 (m, 6H), 1058, 954, 1.52-1.34 (m, 2H), 1.23 (d, J =6.4 Hz, 800, 731 cm⁻¹ 3H), 1.18-1.03 (m, 2H), 0.94 (d, J = 6.9 Hz, 3H).¹³C NMR (101 MHz, CDCl₃) δ 171.75, 168.76, 155.39, 148.79, 140.46,130.62, 109.44, 74.90, 56.08, 48.04, 43.11, 42.95, 31.26, 30.67, 25.14,25.00, 18.33, 17.49, 12.53. 164 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz,CDCl₃) δ film) 3369, [M + H]⁺ calcd for 12.17 (s, 1H), 8.58 (t, J = 7.7Hz, 1H), 2971, 1733, C₂₂H₂₉N₂O₅, 7.99 (d, J = 5.2 Hz, 1H), 7.14-6.90 (m,1648, 1527, 401.2071; found, 3H), 6.87 (d, J = 5.3 Hz, 1H), 1438, 1263,401.2072 5.72-5.58 (m, 1H), 4.86-4.71 (m, 1H), 1149, 1057, 3.93 (s, 3H),3.44 (dp, J = 10.5, 7.1 Hz, 1H), 801, 770, 2.42 (d, J = 1.7 Hz, 3H),2.38 (s, 3H), 730 cm⁻¹ 1.61 (dd, J = 14.3, 7.2 Hz, 3H), 1.29 (dd, J =7.1, 2.7 Hz, 3H), 1.10-0.95 (m, 3H). 165 IR (thin HRMS-ESI (m/z) ¹H NMR(400 MHz, CDCl₃) δ film) 3370, [M + H]⁺ calcd for 12.15 (s, 1H),8.69-8.42 (m, 1H), 8.00 (d, J = 5.2 Hz, 2975, 1734, C₂₂H₂₈FN₂O₅, 1H),6.88 (d, J = 5.2 Hz, 1H), 1649, 1527, 419.1977; found 6.70 (ddd, J =14.6, 8.1, 2.5 Hz, 2H), 1480, 1262, 419.1975 5.59 (ddq, J = 12.4, 10.7,6.2 Hz, 1H), 1148, 849, 4.76 (p, J = 7.2 Hz, 1H), 3.94 (d, J = 1.9 Hz,799, 728 cm⁻¹ 3H), 3.38 (dp, J = 10.5, 7.0 Hz, 1H), 2.41 (d, J = 1.9 Hz,3H), 2.36 (s, 3H), 1.61 (dd, J = 13.6, 7.2 Hz, 3H), 1.27 (dd, J = 7.1,3.1 Hz, 3H), 1.04 (dt, J = 11.6, 6.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ−118.25, −118.31. 166 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δfilm) 3369, [M + H]⁺ calcd for 12.16 (d, J = 3.9 Hz, 1H), 8.56 (t, J =7.7 Hz, 2971, 1733, C₂₂H₂₉N₂O₅, 1H), 8.00 (d, J = 5.2 Hz, 1H), 1648,1527, 401.2071; found, 7.07-6.90 (m, 3H), 6.88 (d, J = 5.2 Hz, 1H),1438, 1280, 401.2066 5.73-5.53 (m, 1H), 4.76 (pd, J = 7.2, 1263, 1149,1.1 Hz, 1H), 3.95 (s, 3H), 3.43 (dp, J = 10.5, 1056, 801, 7.2 Hz, 1H),2.42 (d, J = 1.9 Hz, 770, 730 cm⁻¹ 3H), 2.38 (s, 3H), 1.61 (dd, J =14.3, 7.2 Hz, 3H), 1.29 (dd, J = 7.2, 2.3 Hz, 3H), 1.06 (t, J = 6.0 Hz,3H). 167 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 3370,[M + H]⁺ calcd for 12.15 (d, J = 3.3 Hz, 1H), 8.55 (t, J = 7.9 Hz, 2976,1734, C₂₂H₂₈FN₂O₅, 1H), 8.00 (d, J = 5.2 Hz, 1H), 6.88 (d, J = 5.2 Hz,1649, 1527, 401.1977; found, 1H), 6.70 (ddd, J = 15.1, 9.4, 1480, 1263,419.1971 2.6 Hz, 2H), 5.59 (ddq, J = 12.4, 10.5, 1149, 849, 6.2 Hz, 1H),4.76 (p, J = 7.3 Hz, 1H), 800, 730 cm⁻¹ 3.95 (s, 3H), 3.38 (dp, J =10.5, 7.0 Hz, 1H), 2.41 (d, J = 1.9 Hz, 3H), 2.36 (s, 3H), 1.61 (dd, J =13.6, 7.2 Hz, 3H), 1.27 (dd, J = 7.2, 2.9 Hz, 3H), 1.05 (t, J = 5.9 Hz,3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −118.26, −118.27, −118.33. 168 IR (thinHRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 3370, [M + H]⁺ calcd for12.16 (d, J = 3.8 Hz, 1H), 8.56 (t, J = 7.6 Hz, 2971, 1734, C₂₂H₂₉N₂O₅,1H), 8.01 (d, J = 5.2 Hz, 1H), 1649, 1527, 401.2071; found, 7.05-6.91(m, 3H), 6.88 (d, J = 5.2 Hz, 1H), 1451, 1263, 401.2070 5.70-5.57 (m,1H), 4.76 (pd, J = 7.1, 1150, 801, 1.1 Hz, 1H), 3.95 (s, 3H), 3.43 (dp,J = 10.5, 770, 730 cm⁻¹ 7.2 Hz, 1H), 2.42 (d, J = 2.0 Hz, 3H), 2.38 (s,3H), 1.61 (dd, J = 14.3, 7.2 Hz, 3H), 1.29 (dd, J = 7.2, 2.1 Hz, 3H),1.06 (t, J = 6.0 Hz, 3H). 169 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz,CDCl₃) δ film) 3371, [M + H]⁺ calcd for 12.15 (d, J = 3.3 Hz, 1H), 8.55(t, J = 7.8 Hz, 2976, 1734, C₂₂H₂₈FN₂O₅, 1H), 8.00 (d, J = 5.2 Hz, 1H),6.88 (d, J = 5.2 Hz, 1649, 1527, 419.1977; found, 1H), 6.70 (ddd, J =17.0, 9.4, 1480, 1280, 419.1971 2.8 Hz, 2H), 5.59 (ddq, J = 12.2, 10.8,1262, 1157, 6.2 Hz, 1H), 4.76 (p, J = 7.3 Hz, 1H), 849, 800, 3.95 (s,3H), 3.38 (dp, J = 10.4, 7.0 Hz, 731 cm⁻¹ 1H), 2.41 (d, J = 2.2 Hz, 3H),2.36 (s, 3H), 1.61 (dd, J = 13.6, 7.2 Hz, 3H), 1.27 (dd, J = 7.2, 2.8Hz, 3H), 1.05 (t, J = 5.9 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −118.29,−118.36. 170 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ [M + H]⁺ calcd for12.16 (s, 1H), 8.41 (d, J = 7.9 Hz, 1H), C₂₁H₂₇N₂O₆, 7.97 (d, J = 5.2Hz, 1H), 7.23-7.10 (m, 403.1864; found, 2H), 6.92-6.78 (m, 3H), 5.31(dq, J = 7.8, 403.1827 6.3 Hz, 1H), 4.63-4.49 (m, 1H), 3.93 (s, 3H),3.81 (s, 3H), 3.49-3.39 (m, 1H), 1.26 (d, J = 6.3 Hz, 3H), 1.23 (d, J =7.2 Hz, 3H), 1.16 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.5,168.6, 157.2, 155.3, 148.7, 140.4, 131.1, 130.6, 128.1, 127.4, 120.5,110.5, 109.4, 75.1, 56.0, 55.4, 48.0, 37.6, 17.9, 17.8, 16.6. 171 IR(thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ film) 2978, [M + H]⁺calcd for 12.16 (s, 1H), 8.50 (d, J = 8.0 Hz, 1H), 2937, 1733,C₂₀H₂₅N₂O₅, 8.01 (d, J = 5.2 Hz, 1H), 7.32-7.27 (m, 1647, 1527,373.1758; found, 2H), 7.24-7.16 (m, 3H), 6.88 (d, J = 5.2 Hz, 1451,1262, 373.1752 1H), 5.11 (dq, J = 7.7, 6.3 Hz, 1147, 701 cm⁻¹ 1H),4.77-4.67 (m, 1H), 3.95 (s, 3H), 2.97-2.87 (m, 1H), 1.54 (d, J = 7.2 Hz,3H), 1.31 (d, J = 7.0 Hz, 3H), 1.13 (d, J = 6.3 Hz, 3H). ¹³C NMR (126MHz, CDCl₃) δ 171.8, 168.7, 155.3, 148.7, 142.9, 140.5, 130.4, 128.5,127.8, 126.8, 109.4, 76.5, 56.1, 48.1, 44.9, 18.4, 18.2, 17.2. 172 IR(thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ film) 3368, [M + H]⁺calcd for 12.16 (s, 1H), 8.50 (d, J = 7.9 Hz, 1H), 2978, 1937,C₁₉H₂₅N₂O₅S, 8.00 (d, J = 5.2 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1734, 1648,393.1479; found, 1H), 6.61 (d, J = 3.5 Hz, 1H), 6.55 (dq, 1527, 1480,393.1473 J = 3.5, 1.1 Hz, 1H), 5.10-5.01 (m, 1438, 1262, 1H), 4.77-4.67(m, 1H), 3.95 (s, 3H), 797, 730 cm⁻¹ 3.22-3.12 (m, 1H), 2.42 (d, J = 1.1Hz, 3H), 1.55 (d, J = 7.1 Hz, 3H), 1.33 (d, J = 7.0 Hz, 3H), 1.20 (d, J= 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.6, 168.7, 155.3, 148.7,143.3, 140.5, 138.0, 130.5, 124.5, 124.1, 109.4, 76.1, 56.1, 48.1, 40.1,18.4, 17.8, 17.2, 15.3. 173 IR (thin HRMS-ESI (m/z) ¹H NMR (500 MHz,CDCl₃) δ film) 3369, [M + H]⁺ calcd for 12.19 (s, 1H), 8.49 (d, J = 7.9Hz, 1H), 2977, 2939, C₂₁H₂₆FN₂O₆, 8.01 (d, J = 5.2 Hz, 1H), 7.13-7.06(m, 1733, 1649, 421.1769; found, 1H), 6.88 (d, J = 5.3 Hz, 1H), 1528,1450, 421.1770 6.62-6.54 (m, 2H), 5.21-5.12 (m, 1H), 1278, 1262,4.73-4.63 (m, 1H), 3.95 (s, 3H), 3.79 (s, 1149, 952 cm⁻¹ 3H), 3.42-3.32(m, 1H), 1.51 (d, J = 7.2 Hz, 3H), 1.24 (d, J = 7.0 Hz, 3H), 1.14 (d, J= 6.3 Hz, 3H). ¹⁹F NMR (471 MHz, CDCl₃) δ −113.8-−113.9 (m). 174 ESIMSm/z 387.3 ¹H NMR (400 MHz, CDCl₃) δ [(M + H)+] 12.16 (d, J = 4.9 Hz,1H), 8.50 (d, J = 7.8 Hz, 1H), 8.01 (dd, J = 5.2, 2.7 Hz, 1H), 7.21-7.01(m, 4H), 6.88 (dd, J = 5.3, 1.9 Hz, 1H), 5.18 (dq, J = 8.3, 6.3 Hz, 1H),4.73 (p, J = 7.3 Hz, 1H), 3.95 (d, J = 1.6 Hz, 3H), 3.19 (dq, J = 9.0,6.9 Hz, 1H), 2.35 (s, 3H), 1.55 (d, J = 7.0 Hz, 3H), 1.26 (dd, J = 6.9,3.8 Hz, 3H), 1.13 (dd, J = 9.0, 6.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ171.85, 168.74, 155.41, 148.80, 141.65, 140.49, 135.53, 130.54, 126.37,126.31, 126.29, 109.46, 56.07, 53.40, 48.00, 39.74, 19.94, 18.28, 18.27,17.52, −0.01. 175 ¹H NMR (400 MHz, CDCl₃) δ 12.16 (d, J = 0.6 Hz, 1H),8.51 (d, J = 7.9 Hz, 1H), 8.00 (d, J = 5.2 Hz, 1H), 7.22-7.02 (m, 5H),6.88 (d, J = 5.2 Hz, 1H), 5.16 (dq, J = 8.3, 6.2 Hz, 1H), 4.78-4.65 (m,1H), 3.95 (s, 3H), 3.20 (dq, J = 8.3, 6.9 Hz, 1H), 2.35 (s, 3H), 1.56(d, J = 7.2 Hz, 3H), 1.26 (d, J = 6.9 Hz, 3H), 1.15 (d, J = 6.3 Hz, 3H).176 ESIMS m/z 416 ¹H NMR (300 MHz, CDCl₃) δ ([M + H]⁺) 12.18 (s, 1H),8.52 (d, J = 7.9 Hz, 1H), 8.00 (d, J = 5.2 Hz, 1H), 7.13-7.01 (m, 2H),6.88 (d, J = 5.2 Hz, 1H), 6.67 (d, J = 8.5 Hz, 2H), 5.12-4.98 (m, 1H),4.72 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H), 2.92 (s, 6H), 2.88-2.75 (m, 1H),1.57 (s, 3H), 1.26 (dd, J = 7.1, 4.0 Hz, 3H), 1.11 (d, J = 6.2 Hz, 3H).¹³C NMR (75 MHz, CDCl₃) δ 148.75, 140.49, 130.54, 128.42, 112.68,109.42, 40.70, 18.33 (d, J = 22.8 Hz), 0.01. 177 HRMS-ESI (m/z) ¹H NMR(500 MHz, CDCl₃) δ 8.57 (s, [M + H]⁺ calcd for 1H), 8.34 (d, J = 5.4 Hz,1H), 7.07 (d, J = 8.6 Hz, C₂₄H₃₀N₂O₆, 1H), 7.01 (d, J = 5.5 Hz, 1H),443.2177; found, 6.97 (d, J = 6.7 Hz, 2H), 5.12 (dq, J = 8.5, 443.21706.3 Hz, 1H), 4.78-4.67 (m, 1H), 3.91 (s, 3H), 3.19-3.09 (m, 1H), 2.41(s, 3H), 2.31 (s, 3H), 2.28 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H), 1.23 (d,J = 6.9 Hz, 3H), 1.11 (d, J = 6.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ172.41, 168.96, 162.36, 159.42, 146.70, 141.53, 138.75, 137.46, 135.67,135.33, 131.26, 126.95, 126.26, 109.75, 76.48, 56.29, 48.16, 39.45,20.89, 20.78, 19.90, 18.76, 18.48, 17.67. 178 HRMS-ESI (m/z) ¹H NMR (500MHz, CDCl₃) δ 8.57 (s, [M + H]⁺ calcd for 1H), 8.35 (d, J = 5.5 Hz, 1H),7.07 (d, J = 7.7 Hz, C₂₄H₃₀N₂O₆, 1H), 7.01 (d, J = 5.5 Hz, 1H),443.2177; found, 6.98 (d, J = 7.4 Hz, 2H), 5.12 (dq, J = 8.5, 443.21726.2 Hz, 1H), 4.72 (p, J = 7.2 Hz, 1H), 3.91 (s, 3H), 3.18-3.09 (m, 1H),2.41 (s, 3H), 2.31 (s, 3H), 2.27 (s, 3H), 1.50 (d, J = 7.2 Hz, 3H), 1.22(d, J = 6.9 Hz, 3H), 1.10 (d, J = 6.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃)δ 172.41, 168.97, 162.40, 159.43, 146.70, 141.52, 138.72, 137.46,135.64, 135.37, 131.24, 126.98, 126.27, 109.75, 76.37, 56.29, 48.04,39.38, 20.88, 20.78, 19.92, 18.59, 18.24, 17.73. 179 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ 8.51 (s, [M + H]⁺ calcd for 1H), 8.33 (d, J = 5.4Hz, 1H), C₂₆H₃₄N₂O₆, 7.09-7.04 (m, 1H), 7.02-6.94 (m, 3H), 471.2490;found, 5.11 (dq, J = 8.5, 6.2 Hz, 1H), 4.73 (p, J = 7.2 Hz, 471.24841H), 3.89 (s, 3H), 3.19-3.09 (m, 1H), 2.96 (p, J = 7.0 Hz, 1H), 2.31 (s,3H), 2.28 (s, 3H), 1.51 (d, J = 7.2 Hz, 3H), 1.36 (dd, J = 7.0, 1.4 Hz,5H), 1.23 (d, J = 6.9 Hz, 3H), 1.11 (d, J = 6.2 Hz, 3H). ¹³C NMR (126MHz, CDCl₃) δ 174.73, 172.50, 162.34, 159.40, 146.59, 141.90, 138.78,137.63, 135.66, 135.33, 131.25, 126.95, 126.28, 109.58, 76.41, 56.29,48.13, 39.45, 33.94, 20.89, 19.90, 18.80, 18.48, 17.66. 180 HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.50 (s, [M + H]⁺ calcd for 1H), 8.34(d, J = 5.4 Hz, 1H), 7.07 (d, J = 7.8 Hz, C₂₆H₃₄N₂O₆, 1H), 7.03-6.93 (m,3H), 471.2490; found, 5.12 (dq, J = 8.5, 6.2 Hz, 1H), 4.72 (p, 471.2490J = 7.1 Hz, 1H), 3.89 (s, 3H), 3.20-3.09 (m, 1H), 2.96 (p, J = 7.0 Hz,1H), 2.31 (s, 3H), 2.27 (s, 3H), 1.49 (d, J = 7.1 Hz, 3H), 1.37 (dd, J =6.9, 2.0 Hz, 6H), 1.22 (d, J = 6.9 Hz, 3H), 1.09 (d, J = 6.2 Hz, 3H).¹³C NMR (126 MHz, CDCl₃) δ 174.74, 172.50, 162.39, 159.41, 146.59,141.90, 138.76, 137.63, 135.63, 135.37, 131.23, 126.98, 126.28, 109.58,76.29, 56.29, 48.03, 39.40, 33.94, 20.88, 19.91, 18.81, 18.59, 18.25,17.74. 181 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.37 (s, [M + H]⁺calcd for 1H), 8.33 (d, J = 5.4 Hz, 1H), 7.17 (dd, C₂₃H₂₇FN₂O₆, J = 8.4,5.9 Hz, 1H), 7.01 (d, J = 5.4 Hz, 447.1926; found, 1H), 6.84-6.75 (m,2H), 5.10 (p, 447.1923 J = 6.4 Hz, 1H), 4.57 (p, J = 7.2 Hz, 1H), 3.91(s, 3H), 3.22 (p, J = 7.0 Hz, 1H), 2.40 (s, 2H), 2.33 (s, 3H), 1.34 (d,J = 7.1 Hz, 2H), 1.27-1.18 (m, 6H). ¹³C NMR (126 MHz, CDCl₃) δ 171.87,168.95, 162.24, 161.89, 159.95, 159.44, 146.62, 141.38, 138.44, 137.47,136.77, 127.73, 116.74, 116.58, 112.79, 112.62, 109.75, 75.32, 56.29,47.87, 38.50, 20.76, 19.89, 18.40, 17.06, 16.72. 182 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ 8.53 (s, [M + H]⁺ calcd for 1H), 8.35 (d, J = 5.5Hz, 1H), C₂₂H₂₅FN₂O₆, 7.22-7.13 (m, 2H), 7.05-6.93 (m, 3H), 433.1769;found, 5.05 (h, J = 6.5 Hz, 1H), 4.71 (ddt, J = 14.7, 433.1767 10.3, 5.3Hz, 1H), 3.91 (s, 3H), 2.91 (p, J = 6.8 Hz, 1H), 2.41 (s, 3H), 1.48 (d,J = 7.2 Hz, 3H), 1.27 (d, J = 7.2 Hz, 3H), 1.08 (d, J = 6.3 Hz, 3H). ¹³CNMR (126 MHz, CDCl₃) δ 170.34, 167.06, 160.68, 160.54, 158.74, 157.59,144.78, 139.51, 136.64, 136.61, 135.58, 127.40, 127.34, 113.37, 113.21,107.93, 73.96, 54.42, 46.14, 42.14, 18.85, 16.52, 15.76, 15.38. 183HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.56 (s, [M + H]⁺ calcd for1H), 8.35 (d, J = 5.4 Hz, 1H), 7.09 (d, J = 8.4 Hz, C₂₄H₃₀N₂O₇, 1H),7.02 (d, J = 5.5 Hz, 1H), 459.2126; found, 6.75-6.66 (m, 2H), 5.15-5.05(m, 459.2096 1H), 4.72 (pd, J = 7.3, 1.5 Hz, 1H), 3.92 (s, 3H), 3.76 (s,3H), 3.16-3.07 (m, 1H), 2.41 (s, 3H), 2.32 (s, 3H), 1.50 (d, J = 7.2 Hz,3H), 1.22 (d, J = 6.8 Hz, 3H), 1.10 (d, J = 6.3 Hz, 3H). ¹³C NMR (126MHz, CDCl₃) δ 170.45, 167.03, 160.47, 157.55, 155.65, 144.76, 139.57,135.54, 135.02, 132.00, 125.43, 113.97, 109.50, 107.85, 74.52, 54.38,53.17, 46.15, 37.09, 18.83, 18.29, 16.63, 16.24, 15.80. 184 HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.52 (s, [M + H]⁺ calcd for 1H), 8.36(d, J = 5.5 Hz, 1H), C₂₅H₃₁FN₂O₆, 7.11 (ddd, J = 7.5, 5.9, 1.5 Hz, 1H),7.02 (d, 475.2239; found, J = 5.5 Hz, 1H), 6.83 (t, J = 8.1 Hz, 475.22382H), 5.06 (dq, J = 8.1, 6.3 Hz, 1H), 4.66 (dd, J = 9.4, 4.7 Hz, 1H),3.92 (s, 3H), 3.20-3.08 (m, 1H), 2.40 (s, 3H), 2.32 (d, J = 2.3 Hz, 3H),2.29 (td, J = 6.9, 4.8 Hz, 1H), 1.23 (d, J = 6.9 Hz, 3H), 1.11 (d, J =6.2 Hz, 3H), 1.01 (d, J = 6.8 Hz, 3H), 0.93 (d, J = 6.9 Hz, 3H). ¹³C NMR(126 MHz, CDCl₃) δ 171.24, 168.92, 162.74, 161.89, 159.95, 159.47,146.68, 141.59, 137.81, 137.76, 137.49, 127.86, 127.79, 117.00, 116.83,113.00, 112.83, 109.75, 76.14, 57.17, 56.31, 39.04, 31.46, 20.79, 20.00,19.38, 18.45, 17.47, 17.44. 185 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ8.41 (s, [M + H]⁺ calcd for 1H), 8.33 (d, J = 5.4 Hz, 1H), 7.16 (dd,C₂₅H₃₁FN₂O₆, J = 9.0, 5.9 Hz, 1H), 7.01 (d, J = 5.4 Hz, 475.2239; found,1H), 6.81 (t, J = 8.0 Hz, 2H), 475.2236 5.15-5.07 (m, 1H), 4.53 (dd, J =9.5, 4.5 Hz, 1H), 3.90 (s, 3H), 3.24-3.16 (m, 1H), 2.38 (s, 3H), 2.34(s, 3H), 1.88 (td, J = 6.9, 4.5 Hz, 1H), 1.26 (d, J = 6.2 Hz, 3H), 1.21(d, J = 6.9 Hz, 3H) 0.81 (d, J = 6.8 Hz, 3H), 0.63 (d, J = 6.8 Hz, 3H).¹³C NMR (126 MHz, CDCl₃) δ 169.14, 167.00, 160.78, 160.02, 158.08,157.53, 144.77, 139.62, 136.49, 135.51, 135.45, 125.64, 125.57, 114.82,114.66, 110.95, 110.79, 107.84, 73.69, 54.92, 54.40, 36.84, 29.39,18.86, 17.99, 17.09, 15.75, 15.30, 15.12. 186 HRMS-ESI (m/z) ¹H NMR (500MHz, CDCl₃) δ 8.43 (s, [M + H]⁺ calcd for 1H), 8.33 (d, J = 5.4 Hz, 1H),C₂₅H₃₂N₂O₆, 7.24-7.19 (m, 1H), 7.09 (dddd, J = 29.3, 457.2333; found,14.6, 7.2, 2.9 Hz, 3H), 7.00 (d, J = 5.5 Hz, 457.2330 1H), 5.14 (dq, J =8.2, 6.2 Hz, 1H), 4.53 (dd, J = 9.4, 4.3 Hz, 1H), 3.90 (s, 3H), 3.26 (q,J = 7.4 Hz, 1H), 2.38 (s, 3H), 2.36 (s, 3H), 1.91-1.78 (m, 1H), 1.27 (d,J = 6.2 Hz, 3H), 1.25-1.20 (m, 3H), 0.78 (d, J = 6.9 Hz, 3H), 0.58 (d, J= 6.9 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 169.16, 166.97, 160.75,157.48, 144.73, 139.69, 135.46, 134.11, 128.31, 124.26, 124.06, 107.75,73.76, 54.85, 54.36, 37.31, 29.36, 18.84, 17.91, 17.07, 15.67, 15.06,15.00. 187 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.50 (d, [M + H]⁺calcd for J = 9.8 Hz, 1H), 8.35 (d, J = 5.4 Hz, C₂₄H₂₉FN₂O₆, 1H), 7.14(dd, J = 8.6, 5.5 Hz, 2H), 461.2082; found, 7.03 (d, J = 5.5 Hz, 1H),6.94 (t, J = 8.7 Hz, 461.2082 2H), 5.07-4.99 (m, 1H), 4.65 (dd, J = 9.4,4.7 Hz, 1H), 3.92 (s, 3H), 2.93-2.86 (m, 1H), 2.40 (s, 3H), 2.26 (pd, J= 6.8, 4.7 Hz, 1H), 1.28 (d, J = 7.0 Hz, 3H), 1.10 (d, J = 6.3 Hz, 3H),0.99 (d, J = 6.9 Hz, 3H), 0.92 (d, J = 6.9 Hz, 3H). ¹³C NMR (126 MHz,CDCl₃) δ 169.14, 167.00, 160.80, 160.63, 158.69, 157.57, 144.75, 139.63,136.70, 136.67, 135.57, 127.33, 127.27, 113.31, 113.14, 107.86, 74.15,55.24, 54.40, 42.02, 29.52, 18.86, 17.37, 16.09, 15.54, 15.21. 188HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.53 (d, [M + H]⁺ calcd for J =9.3 Hz, 1H), 8.36 (d, J = 5.5 Hz, C₂₆H₃₄N₂O₇, 1H), 7.07 (d, J = 9.5 Hz,1H), 7.02 (d, J = 5.5 Hz, 487.2439; found, 1H), 6.72-6.66 (m, 2H),487.2427 5.06 (dq, J = 8.5, 6.3 Hz, 1H), 4.67 (dd, J = 9.4, 4.6 Hz, 1H),3.91 (s, 3H), 3.76 (s, 3H), 3.15-3.06 (m, 1H), 2.40 (s, 3H), 2.31 (m,4H), 1.23 (d, J = 6.9 Hz, 3H), 1.10 (d, J = 6.2 Hz, 3H), 1.02 (d, J =6.8 Hz, 3H), 0.94 (d, J = 6.9 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ169.38, 167.00, 160.80, 157.51, 155.65, 144.76, 139.71, 135.53, 134.94,132.15, 125.41, 109.49, 107.80, 74.70, 55.25, 54.37, 53.18, 37.08,29.56, 18.86, 18.27, 17.47, 16.60, 15.86, 15.53. 189 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 8.61-8.47 (m, 1H), 8.36 (d, J= 5.4 Hz, 1H), C₂₅H₃₁FN₂O₆, 7.13 (dd, J = 9.6, 5.7 Hz, 1H), 7.02 (d,475.2239; found, J = 5.5 Hz, 1H), 6.88-6.79 (m, 2H), 475.2238 5.09 (dq,J = 8.0, 6.3 Hz, 1H), 4.64 (dd, J = 9.1, 5.0 Hz, 1H), 3.92 (s, 3H), 3.13(p, J = 7.1 Hz, 1H), 2.41 (s, 3H), 2.33 (s, 3H), 2.29 (qd, J = 7.0, 5.2Hz, 1H), 1.23 (d, J = 7.0 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H), 0.99 (d, J= 6.8 Hz, 3H), 0.96 (d, J = 6.9 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ169.44, 167.00, 160.79, 159.96, 158.02, 157.53, 144.78, 139.68, 135.91,135.53, 135.50, 125.99, 125.93, 115.05, 114.89, 111.11, 110.95, 107.83,73.93, 55.11, 54.38, 37.14, 29.57, 18.86, 18.10, 17.03, 16.32, 16.00,15.50. 190 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.40 (s, [M + H]⁺calcd for 1H), 8.34 (d, J = 5.4 Hz, 1H), 7.18 (dd, C₂₅H₃₁FN₂O₆, J = 9.5,5.8 Hz, 1H), 7.02 (d, J = 5.5 Hz, 475.2239; found, 1H), 6.84-6.75 (m,2H), 5.10 (p, 475.2235 J = 6.4 Hz, 1H), 4.51 (dd, J = 9.2, 5.1 Hz, 1H),3.92 (s, 3H), 3.22 (p, J = 7.1 Hz, 1H), 2.40 (s, 3H), 2.33 (s, 3H), 2.15(pd, J = 6.9, 5.0 Hz, 1H), 1.23 (d, J = 7.1 Hz, 3H), 1.21 (d, J = 6.3Hz, 3H), 0.88 (d, J = 6.9 Hz, 3H), 0.84 (d, J = 6.9 Hz, 3H). ¹³C NMR(126 MHz, CDCl₃) δ 170.81, 168.93, 162.52, 161.93, 159.99, 159.45,146.63, 141.52, 138.48, 138.42, 137.46, 136.82, 136.79, 127.88, 127.82,116.75, 116.59, 112.77, 112.61, 109.71, 75.30, 57.02, 56.30, 38.43,31.44, 20.78, 19.90, 18.78, 17.72, 17.08, 16.67. 191 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ 8.42 (s, [M + H]⁺ calcd for 1H), 8.35 (d, J = 5.4Hz, 1H), 7.23 (dd, C₂₅H₃₂N₂O₆, J = 7.8, 1.4 Hz, 1H), 7.15-7.03 (m,457.2333; found, 3H), 7.02 (d, J = 5.4 Hz, 1H), 5.13 (p, J = 6.4 Hz,457.2331 1H), 4.53 (dd, J = 9.2, 4.9 Hz, 1H), 3.91 (s, 3H), 3.28 (p, J =7.1 Hz, 1H), 2.40 (s, 3H), 2.36 (s, 3H), 2.14 (pd, J = 6.9, 4.9 Hz, 1H),1.26 (d, J = 7.2 Hz, 3H), 1.22 (d, J = 6.3 Hz, 3H), 0.86 (d, J = 6.9 Hz,3H), 0.81 (d, J = 6.9 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 170.77,168.93, 162.52, 159.43, 146.63, 141.61, 141.09, 137.44, 136.15, 130.25,126.37, 126.20, 126.09, 109.69, 75.37, 57.02, 56.29, 38.88, 31.51,20.79, 19.83, 18.77, 17.70, 16.91, 16.26. 192 HRMS-ESI (m/z) ¹H NMR (500MHz, CDCl₃) δ [M + H]⁺ calcd for 8.58-8.45 (m, 1H), 8.36 (d, J = 5.5 Hz,1H), C₂₄H₂₉FN₂O₆, 7.16 (ddd, J = 10.8, 6.6, 3.7 Hz, 2H), 457.2333;found, 7.02 (d, J = 5.5 Hz, 1H), 457.2331 7.01-6.94 (m, 2H), 5.10-4.99(m, 1H), 4.63 (dd, J = 9.2, 5.0 Hz, 1H), 3.92 (s, 3H), 2.90 (p, J = 7.1Hz, 1H), 2.40 (d, J = 2.1 Hz, 3H), 2.31-2.21 (m, 1H), 1.28 (d, J = 7.0Hz, 3H), 1.09 (d, J = 6.4 Hz, 3H), 1.00-0.97 (m, 3H), 0.96 (d, J = 6.9Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.25, 168.93, 162.72, 162.58,160.64, 159.46, 146.69, 141.58, 138.61, 138.59, 137.46, 129.30, 129.23,115.28, 115.11, 109.76, 75.84, 57.06, 56.31, 44.06, 31.47, 20.79, 18.93,17.96, 17.84, 17.26. 193 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M +H]⁺ calcd for 8.62-8.50 (m, 1H), 8.36 (d, J = 5.4 Hz, 1H), C₂₆H₃₄N₂O₇,7.10 (d, J = 8.4 Hz, 1H), 7.02 (d, J = 5.5 Hz, 487.2439; found, 1H),6.75-6.67 (m, 2H), 487.2434 5.09 (dq, J = 8.4, 6.3 Hz, 1H), 4.65 (dd, J= 9.1, 4.9 Hz, 1H), 3.91 (s, 3H), 3.75 (s, 3H), 3.17-3.06 (m, 1H), 2.40(s, 3H), 2.32 (m, 4H), 1.22 (d, J = 6.9 Hz, 3H), 1.11 (d, J = 6.2 Hz,3H), 0.99 (d, J = 6.8 Hz, 3H), 0.97 (d, J = 6.9 Hz, 3H). ¹³C NMR (126MHz, CDCl₃) δ 169.50, 167.02, 160.80, 157.52, 155.67, 144.82, 139.74,135.53, 135.01, 132.08, 125.49, 114.01, 109.51, 107.84, 74.46, 55.12,54.40, 53.18, 37.11, 29.65, 18.89, 18.31, 17.06, 16.41, 16.02, 15.83.194 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for8.45-8.36 (m, 1H), 8.33 (d, J = 5.5 Hz, 1H), C₂₃H₂₈N₂O₆, 7.25-7.17 (m,1H), 7.17-7.03 (m, 429.2020; found, 3H), 7.01 (d, J = 5.5 Hz, 1H),429.2021 5.18-5.09 (m, 1H), 4.61-4.48 (m, 1H), 3.91 (s, 3H), 3.28 (p, J= 7.3 Hz, 1H), 2.39 (d, J = 5.8 Hz, 3H), 2.36 (s, 3H), 1.32 (d, J = 7.2Hz, 3H), 1.26 (d, J = 7.0 Hz, 3H), 1.23 (d, J = 6.3 Hz, 3H). ¹³C NMR(126 MHz, CDCl₃) δ 169.93, 167.04, 160.36, 157.55, 144.72, 139.53,139.14, 135.53, 134.21, 128.32, 124.37, 124.31, 107.85, 73.52, 54.40,46.07, 37.09, 18.84, 17.93, 16.51, 15.05, 14.45. 195 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ 8.54 (d, [M + H]⁺ calcd for J = 7.4 Hz, 1H), 8.34(d, J = 5.4 Hz, C₂₃H₂₇FN₂O₆, 1H), 7.13 (dd, J = 9.5, 5.8 Hz, 1H),447.1926; found, 7.02 (d, J = 5.5 Hz, 1H), 447.1922 6.88-6.81 (m, 2H),5.09 (dq, J = 8.2, 6.3 Hz, 1H), 4.72 (p, J = 7.3 Hz, 1H), 3.91 (s, 3H),3.20-3.09 (m, 1H), 2.41 (s, 3H), 2.33 (s, 3H), 1.50 (d, J = 7.1 Hz, 3H),1.23 (d, J = 6.8 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz,CDCl₃) δ 170.39, 167.02, 160.44, 159.98, 158.04, 157.54, 144.76, 139.53,135.94, 135.88, 135.55, 135.49, 125.94, 125.88, 115.11, 114.94, 111.06,110.90, 107.87, 74.14, 54.38, 46.21, 37.21, 18.84, 18.08, 16.77, 16.43,15.46. 196 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.44 (s, [M + H]⁺calcd for 1H), 8.34 (d, J = 5.4 Hz, 1H), C₂₄H₂₉FN₂O₆, 7.12 (ddd, J =9.3, 4.5, 2.0 Hz, 1H), 7.00 (d, 461.2082; found, J = 5.5 Hz, 1H), 6.86(dd, J = 9.0, 6.7 Hz, 461.2082 2H), 5.12 (dq, J = 7.9, 6.3 Hz, 1H), 4.18(dd, J = 5.7, 2.8 Hz, 2H), 3.90 (s, 3H), 3.14 (p, J = 7.1 Hz, 1H), 2.95(p, J = 7.0 Hz, 1H), 2.32 (s, 3H), 1.37 (d, J = 7.0 Hz, 6H), 1.22 (d, J= 7.0 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ174.71, 169.37, 163.02, 161.95, 160.00, 159.48, 146.62, 141.68, 137.91,137.73, 137.35, 137.32, 127.89, 127.82, 117.05, 116.89, 113.04, 112.87,109.72, 76.09, 56.31, 41.38, 39.11, 33.98, 20.01, 18.81, 18.22, 17.42.197 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.34 (d, [M + H]⁺ calcd forJ = 5.0 Hz, 1H), 8.32 (d, J = 5.4 Hz, C₂₄H₂₉FN₂O₆, 1H), 7.21-7.10 (m,1H), 6.99 (d, J = 5.4 Hz, 461.2082; found, 1H), 6.84-6.76 (m, 2H),461.2082 5.13 (p, J = 6.4 Hz, 1H), 4.17-3.92 (m, 2H), 3.90-3.88 (s, 3H),3.22 (p, J = 7.1 Hz, 1H), 2.94 (p, J = 7.0 Hz, 1H), 2.33 (s, 3H) 1.36 (dJ = 7.0 Hz, 6H) 1.23 (dd, J = 6.7, 1.3 Hz, 6H). ¹³C NMR (126 MHz, CDCl₃)δ 174.69, 169.03, 162.91, 161.95, 160.01, 159.46, 146.58, 141.61,138.48, 137.71, 136.72, 136.69, 127.84, 127.77, 116.78, 116.62, 112.83,112.67, 109.70, 75.49, 56.30, 41.22, 38.58, 33.96, 19.87, 19.86, 18.80,17.11, 16.56. 198 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.33 (m, [M +H]⁺ calcd for 2H), 7.21 (dd, J = 7.6, 1.5 Hz, 1H), C₂₄H₃₀N₂O₆, 7.10(ttd, J = 14.3, 7.8, 7.3, 1.8 Hz, 443.2177; found, 3H), 6.98 (d, J = 5.5Hz, 1H), 5.17 (h, J = 6.5 Hz, 443.2174 1H), 4.14-3.90 (m, 2H), 3.89 (s,3H), 3.33-3.23 (m, 1H), 2.94 (p, J = 7.0 Hz, 1H), 2.35 (s, 3H), 1.36 (d,J = 7.0 Hz, 6H), 1.28-1.19 (m, 6H). ¹³C NMR (126 MHz, CDCl₃) δ 174.69,169.05, 162.90, 159.44, 146.58, 141.67, 141.02, 137.68, 136.17, 130.25,126.30, 126.27, 126.11, 109.66, 75.58, 56.29, 41.22, 39.10, 33.97,19.80, 18.80, 18.75, 17.05, 16.24. 199 HRMS-ESI (m/z) ¹H NMR (500 MHz,CDCl₃) δ 8.44 (t, [M + H]⁺ calcd for J = 5.5 Hz, 1H), 8.33 (d, J = 5.4Hz, C₂₃H₂₇FN₂O₆, 1H), 7.18-7.11 (m, 2H), 447.1926; found, 7.02-6.92 (m,3H), 5.14-5.02 (m, 1H), 447.1926 4.22-4.13 (m, 2H), 3.90 (s, 3H),3.02-2.84 (m, 2H), 1.37 (d, J = 7.0 Hz, 6H), 1.30-1.23 (m, 3H), 1.09 (d,J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.71, 169.27, 163.03,162.63, 160.69, 159.48, 146.62, 141.66, 138.52, 137.74, 129.30, 129.23,115.31, 115.14, 109.73, 76.02, 56.31, 44.12, 41.41, 33.98, 18.81, 17.81,17.26. 200 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.45 (t, [M + H]⁺calcd for J = 5.4 Hz, 1H), 8.33 (d, J = 5.4 Hz, C₂₅H₃₂N₂O₇, 1H), 7.08(d, J = 8.4 Hz, 1H), 7.00 (d, J = 5.5 Hz, 473.2282; found, 1H),6.77-6.67 (m, 2H), 473.2275 5.12 (dq, J = 8.1, 6.2 Hz, 1H), 4.25-4.14(m, 2H), 3.89 (s, 3H), 3.77 (s, 3H), 3.16-3.05 (m, 1H), 2.96 (p, J = 7.0Hz, 1H) 2.31 (s, 3H), 1.37 (d, J = 7.0 Hz, 6H), 1.22 (d, J = 7.0 Hz,3H), 1.12 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.71,169.43, 163.02, 159.46, 157.66, 146.63, 141.71, 137.71, 136.96, 133.86,127.39, 115.94, 111.46, 109.70, 76.54, 56.30, 55.11, 41.41, 39.04,33.98, 20.18, 18.81, 18.27, 17.62. 201 HRMS-ESI (m/z) ¹H NMR (500 MHz,CDCl₃) δ 8.36 (s, [M + H]⁺ calcd for 1H), 8.31 (d, J = 5.4 Hz, 1H),C₂₅H₃₁FN₂O₆, 7.16 (ddd, J = 13.0, 8.8, 6.0 Hz, 1H), 475.2239; found,6.97 (d, J = 5.4 Hz, 1H), 6.81 (t, J = 7.8 Hz, 475.2234 2H), 5.11 (dq, J= 8.3, 6.4 Hz, 1H), 4.56 (p, J = 7.3 Hz, 1H), 3.88 (s, 3H), 3.26-3.16(m, 1H), 2.99-2.90 (m, 1H), 2.34 (s, 3H), 1.35 (d, J = 6.9 Hz, 6H), 1.27(d, J = 6.3 Hz, 3H), 1.21 (d, J = 7.1 Hz, 3H), 1.08 (d, J = 7.1 Hz, 3H).¹³C NMR (126 MHz, CDCl₃) δ 174.68, 172.20, 162.29, 161.91, 159.97,159.42, 146.55, 141.88, 138.36, 138.30, 137.64, 137.22, 137.19, 127.57,127.50, 116.70, 116.54, 112.85, 112.68, 109.58, 75.44, 56.28, 47.83,38.90, 33.93, 19.91, 18.80, 18.20, 17.70, 17.22. 202 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 8.35 (dd, J = 8.2, 5.5 Hz,1H), 8.31 (d, J = 5.4 Hz, C₂₅H₃₂N₂O₆, 1H), 7.19 (dd, J = 7.7, 1.4 Hz,457.2333; found, 1H), 7.09 (ttd, J = 14.5, 7.2, 1.7 Hz, 457.2331 3H),6.97 (d, J = 5.4 Hz, 1H), 5.15 (dq, J = 7.7, 6.1 Hz, 1H), 4.60-4.45 (m,1H), 3.88 (s, 3H), 3.26 (dp, J = 14.7, 7.2 Hz, 1H), 2.93 (p, J = 7.1 Hz,1H), 2.36 (s, 3H), 1.35 (d, J = 7.0 Hz, 6H), 1.28 (d, J = 6.3 Hz, 3H),1.24 (d, J = 7.2 Hz, 3H), 1.01 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz,CDCl₃) δ 174.68, 172.25, 162.27, 159.39, 146.55, 141.96, 141.54, 137.60,136.03, 130.21, 126.16, 125.98, 109.53, 77.28, 75.56, 56.27, 47.84,39.44, 33.93, 19.84, 18.81, 18.14, 17.71, 17.01. 203 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ 8.46 (s, [M + H]⁺ calcd for 1H), 8.33 (d, J = 5.4Hz, 1H), 7.15 (dd, C₂₄H₂₉FN₂O₆, J = 8.6, 5.5 Hz, 2H), 7.01-6.92 (m,461.2082; found, 3H), 5.09-5.00 (m, 1H), 4.71 (p, J = 7.3 Hz, 461.20821H), 3.89 (s, 3H), 3.00-2.86 (m, 2H), 1.47 (d, J = 7.1 Hz, 3H), 1.36(dd, J = 7.0, 1.3 Hz, 6H), 1.27 (d, J = 7.0 Hz, 3H), 1.09 (d, J = 6.3Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.71, 172.30, 162.61, 162.36,160.67, 159.46, 146.57, 141.90, 138.63, 137.71, 129.29, 129.23, 115.27,115.10, 109.62, 75.96, 56.30, 48.10, 44.13, 33.96, 18.81, 18.72, 17.93,17.20. 204 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.50 (d, [M + H]⁺calcd for J = 9.7 Hz, 1H), 8.33 (d, J = 5.4 Hz, C₂₆H₃₄N₂O₇, 1H), 7.09(d, J = 8.3 Hz, 1H), 6.99 (d, J = 5.5 Hz, 487.2439; found, 1H),6.76-6.66 (m, 2H), 487.2431 5.08 (dq, J = 8.3, 6.2 Hz, 1H), 4.73 (p, J =7.3 Hz, 1H), 3.89 (s, 3H), 3.77 (s, 3H), 3.18-3.05 (m, 1H), 2.95 (p, J =7.0 Hz, 1H), 2.32 (s, 3H), 1.50 (d, J = 7.2 Hz, 3H), 1.36 (dd, J = 7.0,1.5 Hz, 6H), 1.22 (d, J = 6.8 Hz, 3H), 1.11 (d, J = 6.3 Hz, 3H). ¹³C NMR(126 MHz, CDCl₃) δ 174.70, 172.48, 162.36, 159.43, 157.65, 146.58,141.96, 137.67, 136.91, 134.03, 127.40, 115.92, 111.45, 109.59, 76.46,56.29, 55.12, 48.15, 39.14, 33.95, 20.19, 18.81, 18.43, 17.63. 205HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 8.51-8.39(m, 1H), 8.34 (d, J = 5.3 Hz, 1H), C₂₅H₃₁FN₂O₆, 7.13 (dd, J = 9.4, 5.8Hz, 1H), 6.99 (d, 475.2239; found, J = 5.4 Hz, 1H), 6.87-6.81 (m, 2H),475.2239 5.09 (dq, J = 7.9, 6.2 Hz, 1H), 4.71 (p, J = 7.3 Hz, 1H), 3.89(s, 3H), 3.13 (p, J = 7.1 Hz, 1H), 2.95 (p, J = 7.0 Hz, 1H), 2.33 (s,3H), 1.48 (d, J = 7.1 Hz, 3H), 1.39-1.33 (m, 6H), 1.22 (d, J = 6.9 Hz,3H), 1.10 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.71,172.43, 162.41, 161.91, 159.97, 159.46, 146.57, 141.90, 137.88, 137.82,137.47, 127.91, 127.85, 117.01, 116.84, 113.03, 112.87, 109.63, 75.88,56.30, 48.01, 39.13, 33.96, 20.02, 18.81, 18.50, 18.12, 17.48. 206HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 8.35-8.27(m, 2H), 7.22 (dd, J = 7.7, 1.4 Hz, C₂₅H₃₂N₂O₆, 1H), 7.17-7.03 (m, 3H),6.98 (d, J = 5.4 Hz, 457.2333; found, 1H), 5.14 (p, J = 6.5 Hz, 1H),457.2332 4.56 (p, J = 7.2 Hz, 1H), 3.89 (s, 3H), 3.28 (p, J = 7.0 Hz,1H), 2.94 (p, J = 7.0 Hz, 1H), 2.35 (s, 3H), 1.39-1.34 (m, 6H) 1.31 (d,J = 7.2 Hz, 3H), 1.25 (d, J = 7.1 Hz, 3H), 1.22 (d, J = 6.4 Hz, 3H). ¹³CNMR (126 MHz, CDCl₃) δ 174.70, 171.97, 162.25, 159.43, 146.50, 141.92,141.08, 137.66, 136.14, 130.23, 126.33, 126.21, 126.09, 109.55, 75.33,56.29, 47.95, 39.03, 33.95, 19.82, 18.81, 18.47, 16.96, 16.35. 207HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.45 (s, [M + H]⁺ calcd for1H), 8.33 (d, J = 5.4 Hz, 1H), C₂₄H₂₉FN₂O₆, 7.20-7.12 (m, 2H), 7.02-6.94(m, 3H), 461.2082; found, 5.10-4.99 (m, 1H), 4.70 (p, J = 7.3 Hz,461.2082 1H), 3.89 (s, 3H), 2.94 (ddt, J = 15.3, 14.2, 7.1 Hz, 2H), 1.47(d, J = 7.1 Hz, 3H), 1.38-1.34 (m, 6H), 1.27 (d, J = 6.9 Hz, 3H), 1.07(d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.72, 172.36, 162.62,162.44, 160.67, 159.46, 146.57, 141.88, 138.58, 137.70, 129.33, 129.26,115.28, 115.11, 109.63, 75.77, 56.30, 48.03, 44.07, 33.96, 18.81, 18.46,17.65, 17.30. 208 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.49 (d, [M +H]⁺ calcd for J = 5.7 Hz, 1H), 8.34 (d, J = 5.5 Hz, C₂₆H₃₄N₂O₇, 1H),7.09 (d, J = 8.3 Hz, 1H), 6.99 (d, J = 5.4 Hz, 487.2439; found, 1H),6.75-6.67 (m, 2H), 487.2432 5.09 (dq, J = 8.2, 6.2 Hz, 1H), 4.72 (p, J =7.2 Hz, 1H), 3.89 (s, 3H), 3.76 (s, 3H), 3.15-3.05 (m, 1H), 2.96 (p, J =7.0 Hz, 1H), 2.32 (s, 3H), 1.49 (d, J = 7.2 Hz, 3H), 1.39-1.34 (m, 6H),1.21 (d, J = 6.9 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz,CDCl₃) δ 174.71, 172.49, 162.41, 159.44, 157.62, 146.58, 141.96, 137.67,136.95, 134.00, 127.40, 115.94, 111.45, 109.60, 76.36, 56.29, 55.10,48.06, 39.08, 33.96, 20.21, 18.82, 18.58, 18.19, 17.74. 209 HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.44 (d, [M + H]⁺ calcd for J = 9.0 Hz,1H), 8.34 (d, J = 5.4 Hz, C₂₇H₃₅FN₂O₆, 1H), 7.16-7.08 (m, 1H), 6.99 (d,J = 5.5 Hz, 503.2552; found, 1H), 6.82 (t, J = 7.9 Hz, 2H), 503.25475.06 (dq, J = 8.0, 6.2 Hz, 1H), 4.66 (dd, J = 9.4, 4.8 Hz, 1H), 3.89 (s,3H), 3.20-3.09 (m, 1H), 2.95 (p, J = 7.0 Hz, 1H), 2.32 (s, 3H), 2.28(qd, J = 7.0, 4.9 Hz, 1H), 1.39-1.32 (m, 6H), 1.23 (d, J = 6.9 Hz, 3H),1.11 (d, J = 6.2 Hz, 3H), 1.01 (d, J = 6.8 Hz, 3H), 0.92 (d, J = 6.8 Hz,3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.67, 171.34, 162.74, 161.92, 159.98,159.45, 146.56, 142.09, 137.82, 137.67, 137.55, 127.90, 127.83, 117.00,116.83, 113.00, 112.84, 109.59, 76.07, 57.14, 56.29, 39.10, 33.94,31.48, 19.99, 19.38, 18.82, 18.47, 17.46. 210 HRMS-ESI (m/z) ¹H NMR (500MHz, CDCl₃) δ 8.32 (m, [M + H]⁺ calcd for 2H), 7.16 (dd, J = 9.5, 5.7Hz, 1H), C₂₇H₃₅FN₂O₇, 6.98 (d, J = 5.5 Hz, 1H), 503.2552; found,6.83-6.76 (m, 2H), 5.10 (dq, J = 8.0, 6.3 Hz, 1H), 503.2554 4.54 (dd, J= 9.4, 4.5 Hz, 1H), 3.88 (s, 3H), 3.19 (p, J = 7.2 Hz, 1H), 2.93 (p, J =7.0 Hz, 1H), 2.34 (s, 3H), 1.88 (pd, J = 6.9, 4.5 Hz, 1H), 1.34 (d, J =7.0 Hz, 6H), 1.25 (d, J = 6.3 Hz, 3H), 1.21 (d, J = 7.1 Hz, 3H), 0.81(d, J = 6.9 Hz, 3H), 0.63 (d, J = 6.9 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃)δ 174.66, 171.16, 162.69, 161.96, 160.03, 159.41, 146.55, 142.06,138.40, 138.34, 137.62, 137.32, 127.61, 116.73, 116.57, 112.86, 112.70,109.54, 75.49, 56.79, 56.28, 38.77, 33.92, 31.34, 19.89, 19.01, 18.82,17.63, 17.17, 17.05. 211 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M +H]⁺ calcd for 8.38-8.27 (m, 2H), 7.21 (dd, J = 7.8, 1.3 Hz, C₂₅H₃₆N₂O₆,1H), 7.09 (dddd, J = 23.7, 14.5, 7.3, 1.6 Hz, 485.2646; found, 3H), 6.97(d, J = 5.5 Hz, 1H), 485.2642 5.14 (dq, J = 6.8, 5.8, 5.3 Hz, 1H), 4.54(dd, J = 9.5, 4.4 Hz, 1H), 3.88 (s, 3H), 3.26 (dp, J = 14.6, 7.1 Hz,1H), 2.93 (p, J = 6.9 Hz, 1H), 2.36 (d, J = 3.7 Hz, 3H), 1.85 (pd, J =6.9, 4.4 Hz, 1H), 1.34 (d, J = 7.0 Hz, 6H), 1.27 (d, J = 6.3 Hz, 3H),1.23 (d, J = 7.1 Hz, 3H), 0.78 (d, J = 6.9 Hz, 3H), 0.58 (d, J = 6.9 Hz,3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.65, 171.20, 162.68, 159.38, 146.55,142.13, 141.63, 137.58, 136.06, 130.25, 126.19, 126.05, 109.49, 75.58,56.75, 56.29, 39.27, 33.92, 31.33, 19.82, 19.02, 18.81, 17.57, 17.02,16.89. 212 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.42 (d, [M + H]⁺calcd for J = 9.0 Hz, 1H), 8.34 (d, J = 5.5 Hz, C₂₆H₃₃FN₂O₆, 1H), 7.14(dd, J = 8.6, 5.5 Hz, 2H), 489.2395; found, 7.00 (d, J = 5.5 Hz, 1H),489.2391 6.97-6.89 (m, 2H), 5.03 (p, J = 6.4 Hz, 1H), 4.65 (dd, J = 9.4,4.7 Hz, 1H), 3.89 (s, 3H), 3.00-2.85 (m, 2H), 2.25 (pd, J = 6.9, 4.7 Hz,1H), 1.38-1.31 (m, 6H), 1.28 (d, J = 7.0 Hz, 3H), 1.09 (d, J = 6.3 Hz,3H), 0.99 (d, J = 6.9 Hz, 3H), 0.91 (d, J = 6.9 Hz, 3H). ¹³C NMR (126MHz, CDCl₃) δ 174.68, 171.17, 162.73, 162.59, 160.64, 159.46, 146.56,142.06, 138.69, 137.69, 129.27, 129.21, 115.23, 115.07, 109.60, 76.00,57.13, 56.30, 43.99, 33.94, 31.47, 19.30, 18.81, 18.02, 17.49, 17.14.213 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.45 (d, [M + H]⁺ calcd forJ = 8.6 Hz, 1H), 8.34 (d, J = 5.5 Hz, C₂₈H₃₈N₂O₇, 1H), 7.07 (d, J = 9.4Hz, 1H), 6.99 (d, J = 5.5 Hz, 515.2752; found, 1H), 6.72-6.65 (m, 2H),515.2737 5.06 (dq, J = 8.3, 6.2 Hz, 1H), 4.67 (dd, J = 9.3, 4.7 Hz, 1H),3.89 (s, 3H), 3.76 (s, 3H), 3.16-3.05 (m, 1H), 2.95 (p, J = 7.0 Hz, 1H),2.35-2.25 (m, 3H), 1.40-1.30 (m, 6H), 1.23 (d, J = 6.9 Hz, 3H), 1.10 (d,J = 6.3 Hz, 3H), 1.01 (d, J = 6.8 Hz, 3H), 0.93 (d, J = 6.9 Hz, 3H). ¹³CNMR (126 MHz, CDCl₃) δ 174.67, 171.40, 162.75, 159.43, 157.63, 146.57,142.14, 137.65, 136.86, 134.14, 127.37, 115.93, 111.45, 109.57, 76.57,60.39, 57.17, 56.29, 55.12, 39.07, 33.94, 31.51, 20.18, 19.40, 18.82,18.54, 17.77, 17.48, 14.20. 214 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ8.44 (d, [M + H]⁺ calcd for J = 9.1 Hz, 1H), 8.35 (d, J = 5.4 Hz,C₂₇H₃₅FN₂O₆, 1H), 7.13 (dd, J = 9.6, 5.8 Hz, 1H), 503.2552; found, 7.00(d, J = 5.4 Hz, 1H), 503.2549 6.88-6.78 (m, 2H), 5.09 (dq, J = 8.1, 6.3Hz, 1H), 4.63 (dd, J = 9.1, 5.2 Hz, 1H), 3.89 (s, 3H), 3.13 (p, J = 7.1Hz, 1H), 2.95 (p, J = 7.0 Hz, 1H), 2.32 (s, 3H), 2.26 (pd, J = 6.8, 4.9Hz, 1H), 1.41-1.31 (m, 6H), 1.23 (d, J = 6.9 Hz, 3H), 1.11 (d, J = 6.3Hz, 3H), 0.99 (d, J = 7.0 Hz, 3H), 0.96 (d, J = 6.9 Hz, 3H). ¹³C NMR(126 MHz, CDCl₃) δ 174.68, 171.48, 162.75, 161.91, 159.97, 159.44,146.59, 142.11, 137.84, 137.64, 137.49, 127.88, 116.98, 116.81, 113.04,112.88, 109.58, 75.80, 57.04, 56.29, 39.14, 33.95, 31.48, 20.01, 19.00,18.81, 18.26, 17.94, 17.46. 215 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ[M + H]⁺ calcd for 8.38-8.28 (m, 2H), 7.25-7.20 (m, 1H), C₂₇H₃₆N₂O₆,7.16-7.02 (m, 3H), 6.99 (d, J = 5.4 Hz, 485.2646; found, 1H), 5.13 (p, J= 6.4 Hz, 1H), 4.53 (dd, 485.2643 J = 9.1, 4.9 Hz, 1H), 3.89 (s, 3H),3.28 (p, J = 7.1 Hz, 1H), 2.94 (h, J = 7.0 Hz, 1H), 2.35 (s, 3H),2.21-2.09 (m, 1H), 1.35 (dd, J = 7.0, 1.2 Hz, 6H), 1.26 (d, J = 7.1 Hz,3H), 1.21 (d, J = 6.2 Hz, 3H), 0.86 (d, J = 6.9 Hz, 3H), 0.81 (d, J =6.9 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.68, 170.88, 162.55, 159.42,146.51, 142.10, 141.12, 137.63, 136.16, 130.26, 126.41, 126.19, 126.09,109.52, 75.28, 57.01, 56.29, 38.91, 33.94, 31.50, 19.81, 18.81, 17.71,16.90, 16.26. 216 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M + H]⁺calcd for 8.48-8.39 (m, 1H), 8.34 (d, J = 5.4 Hz, 1H), C₂₆H₃₃FN₂O₆,7.19-7.11 (m, 2H), 7.03-6.90 (m, 489.2395; found, 3H), 5.05 (m, 1H),4.62 (dd, J = 9.1, 489.2391 5.1 Hz, 1H), 3.89 (s, 3H), 2.92 (dp, J =26.1, 7.0 Hz, 2H), 2.25 (pd, J = 6.9, 4.2 Hz, 1H), 1.38-1.32 (m, 6H),1.27 (d, J = 7.1 Hz, 3H), 1.08 (d, J = 6.2 Hz, 3H), 0.98 (d, J = 6.9 Hz,3H), 0.95 (d, J = 6.9 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.68,171.37, 162.76, 162.61, 160.67, 159.44, 146.59, 142.08, 138.67, 137.64,129.32, 129.26, 115.27, 115.10, 109.59, 75.75, 57.06, 56.30, 44.10,33.95, 31.45, 18.97, 18.81, 17.97, 17.84, 17.27. 217 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ 8.46 (d, [M + H]⁺ calcd for J = 9.0 Hz, 1H), 8.35(d, J = 5.4 Hz, C₂₈H₃₈N₂O₇, 1H), 7.09 (d, J = 8.4 Hz, 1H), 6.99 (d, J =5.5 Hz, 515.2752; found, 1H), 6.75-6.66 (m, 2H), 515.2741 5.09 (dq, J =8.3, 6.2 Hz, 1H), 4.65 (dd, J = 9.1, 5.0 Hz, 1H), 3.89 (s, 3H), 3.75 (s,3H), 3.16-3.04 (m, 1H), 2.95 (p, J = 7.0 Hz, 1H), 2.31 (s, 3H), 2.27(qd, J = 6.9, 5.0 Hz, 1H), 1.39-1.32 (m, 6H), 1.22 (d, J = 6.9 Hz, 3H),1.10 (d, J = 6.3 Hz, 3H), 0.99 (d, J = 6.8 Hz, 3H), 0.96 (d, J = 6.9 Hz,3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.68, 171.52, 162.73, 159.42, 157.61,146.60, 142.18, 137.62, 136.92, 134.06, 127.42, 115.96, 111.44, 109.55,76.31, 57.04, 56.29, 55.10, 39.09, 33.94, 31.54, 20.20, 19.00, 18.82,18.33, 17.94, 17.77. 218 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ [M +H]⁺ calcd for 8.37-8.28 (m, 2H), 7.22-7.12 (m, 1H), C₂₅H₃₁FN₂O₆, 6.99(d, J = 5.5 Hz, 1H), 6.85-6.75 (m, 475.2239; found, 2H), 5.16-5.05 (m,1H), 4.57 (h, J = 7.4 Hz, 475.2236 1H), 3.89 (s, 3H), 3.22 (pd, J = 7.3,4.6 Hz, 1H), 3.00-2.89 (m, 1H), 2.33 (s, 3H), 1.39-1.30 (m, 9H), 1.22(dd, J = 9.8, 6.7 Hz, 6H). ¹³C NMR (126 MHz, CDCl₃) δ 174.70, 171.98,162.25, 161.93, 159.99, 159.45, 146.51, 141.82, 138.46, 137.69, 136.79,136.76, 127.85, 127.79, 116.74, 116.58, 112.79, 112.62, 109.59, 75.24,56.30, 47.88, 38.53, 33.95, 19.88, 18.80, 18.41, 17.05, 16.71. 219HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.48 (d, [M + H]⁺ calcd for J =6.9 Hz, 1H), 8.33 (d, J = 5.3 Hz, C₂₅H₃₁FN₂O₆, 1H), 7.13 (dd, J = 9.4,5.8 Hz, 1H), 475.2239; found, 6.99 (d, J = 5.5 Hz, 1H), 475.22386.88-6.81 (m, 2H), 5.09 (dp, J = 8.1, 6.5 Hz, 1H), 4.72 (p, J = 7.2 Hz,1H), 3.89 (s, 3H), 3.14 (p, J = 7.1 Hz, 1H), 2.95 (p, J = 7.0 Hz 1H),2.33 (d, J = 2.4 Hz, 3H), 1.49 (d, J = 7.1 Hz, 3H), 1.38-1.33 (m, 6H),1.23 (d, J = 6.9 Hz, 3H), 1.11 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz,CDCl₃) δ 174.71, 172.42, 162.36, 161.94, 159.99, 159.45, 146.58, 141.91,137.86, 137.80, 137.69, 137.46, 127.91, 127.84, 117.04, 116.87, 113.00,112.83, 109.62, 75.99, 56.30, 48.11, 39.18, 33.96, 20.00, 19.99, 18.85,18.81, 18.36, 17.37. 220 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.56(s, [M + H]⁺ calcd for 1H), 8.35 (d, J = 5.4 Hz, 1H), 7.09 (d, J = 8.4Hz, C₂₄H₃₀N₂O₇, 1H), 7.02 (d, J = 5.5 Hz, 1H), 459.2126; found,6.77-6.67 (m, 2H), 5.10 (dq, J = 8.3, 459.2103 6.3 Hz, 1H), 4.72 (tt, J= 8.8, 6.2 Hz, 1H), 3.91 (s, 3H), 3.76 (s, 3H), 3.15-3.06 (m, 1H), 2.41(s, 3H), 2.32 (s, 3H), 1.50 (d, J = 7.2 Hz, 3H), 1.22 (d, J = 6.9 Hz,3H), 1.10 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 170.46,167.04, 160.48, 157.55, 155.66, 144.77, 139.57, 135.54, 135.03, 132.01,125.44, 113.97, 109.50, 107.87, 74.52, 54.39, 53.17, 46.15, 37.09,18.84, 18.30, 16.63, 16.25, 15.80. 221 HRMS-ESI (m/z) ¹H NMR (500 MHz,CDCl₃) δ 8.44 (t, [M + H]⁺ calcd for J = 5.4 Hz, 1H), 8.34 (d, J = 5.4Hz, C₂₄H₂₉FN₂O₆, 1H), 7.12 (ddd, J = 10.1, 6.2, 3.4 Hz, 461.2082; found,1H), 7.00 (d, J = 5.5 Hz, 1H), 461.2080 6.90-6.80 (m, 3H), 5.12 (dq, J =7.7, 6.2 Hz, 1H), 4.18 (dd, J = 5.4, 2.8 Hz, 2H), 3.90 (s, 3H), 3.14 (p,J = 7.1 Hz, 1H), 2.95 (p, J = 7.0 Hz, 1H), 2.32 (s, 3H), 1.37 (d, J =7.0 Hz, 6H), 1.22 (d, J = 6.9 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). ¹³C NMR(126 MHz, CDCl₃) δ 174.71, 169.37, 163.02, 161.95, 160.00, 159.48,146.63, 141.67, 137.91, 137.85, 137.73, 137.32, 127.89, 127.82, 117.05,116.89, 113.04, 112.87, 109.72, 76.09, 56.31, 41.38, 39.11, 33.98,20.00, 18.81, 18.71, 18.22, 17.42. 222 HRMS-ESI (m/z) ¹H NMR (500 MHz,CDCl₃) δ [M + H]⁺ calcd for 8.36-8.27 (m, 2H), 7.21 (dd, J = 7.7, 1.4Hz, C₂₄H₃₀N₂O₆, 1H), 7.16-7.05 (m, 3H), 6.98 (d, J = 5.5 Hz, 443.2177;found, 1H), 5.17 (h, J = 6.6 Hz, 1H), 443.2176 4.13-3.89 (m, 2H), 3.89(s, 3H), 3.28 (p, J = 7.1 Hz, 1H), 2.94 (p, J = 7.0 Hz, 1H), 2.35 (s,3H), 1.36 (d, J = 7.0 Hz, 6H), 1.28-1.22 (m, 6H). ¹³C NMR (126 MHz,CDCl₃) δ 174.69, 169.05, 162.90, 159.44, 146.58, 141.67, 141.02, 137.68,136.17, 130.25, 126.29, 126.27, 126.11, 109.66, 75.58, 56.29, 41.22,39.09, 33.97, 19.80, 18.81, 17.05, 16.23. 223 HRMS-ESI (m/z) ¹H NMR (500MHz, CDCl₃) δ 8.44 (t, [M + H]⁺ calcd for J = 5.5 Hz, 1H), 8.33 (d, J =5.4 Hz, C₂₃H₂₇FN₂O₆, 1H), 7.18-7.11 (m, 2H), 447.1926; found, 7.03-6.92(m, 3H), 5.14-5.01 (m, 1H), 4.17 (d, J = 5.4 Hz, 447.1923 2H), 3.90 (s,3H), 3.00-2.86 (m, 2H), 1.37 (d, J = 7.0 Hz, 6H), 1.27 (d, J = 7.0 Hz,3H), 1.09 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.72,169.28, 163.04, 162.64, 160.69, 159.48, 146.62, 141.66, 138.52, 137.74,129.30, 129.24, 115.31, 115.14, 109.73, 76.02, 56.31, 44.12, 41.41,33.98, 18.81, 17.81, 17.26. 224 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ8.45 (t, [M + H]⁺ calcd for J = 5.4 Hz, 1H), 8.33 (d, J = 5.4 Hz,C₂₅H₃₂N₂O₇, 1H), 7.08 (d, J = 8.5 Hz, 1H), 7.00 (d, J = 5.5 Hz,473.2282; found, 1H), 6.76-6.67 (m, 2H), 473.2282 5.12 (dq, J = 8.3, 6.3Hz, 1H), 4.24-4.14 (m, 2H), 3.89 (s, 3H), 3.77 (s, 3H), 3.16-3.05 (m,1H), 2.96 (p, J = 7.0 Hz, 1H) 2.31 (s, 3H) 1.37 (d, J = 7.0 Hz, 6H),1.22 (d, J = 6.9 Hz, 3H), 1.12 (d, J = 6.2 Hz, 3H). ¹³C NMR (126 MHz,CDCl₃) δ 174.71, 169.43, 163.01, 159.46, 157.66, 146.63, 141.71, 137.71,136.96, 133.86, 127.39, 115.94, 111.46, 109.70, 76.54, 56.30, 55.11,41.41, 39.04, 33.98, 20.18, 18.81, 18.27, 17.62. 225 HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ [M + H]⁺ calcd for 8.39-8.28 (m, 2H), 7.24-7.17(m, 1H), C₂₅H₃₂N₂O₆, 7.16-7.02 (m, 3H), 6.98 (d, J = 5.5 Hz, 457.2333;found, 1H), 5.14 (p, J = 6.6 Hz, 1H), 4.55 (dt, 457.2327 J = 10.4, 7.4Hz, 1H), 3.89 (s, 3H), 3.28 (p, J = 7.1 Hz, 1H), 2.94 (p, J = 6.9 Hz,1H), 2.36 (d, J = 4.9 Hz, 3H), 1.36 (dd, J = 7.0, 1.6 Hz, 6H), 1.31 (d,J = 7.1 Hz, 3H), 1.25 (d, J = 7.2 Hz, 3H), 1.22 (d, J = 6.4 Hz, 3H). ¹³CNMR (126 MHz, CDCl₃) δ 174.70, 171.96, 162.25, 159.42, 146.50, 141.92,141.08, 137.65, 136.14, 130.23, 126.33, 126.21, 126.09, 109.55, 75.32,56.29, 47.95, 39.03, 33.95, 19.82, 18.80, 18.47, 16.95, 16.35. 226HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.44 (s, [M + H]⁺ calcd for1H), 8.33 (d, J = 5.4 Hz, 1H), C₂₄H₂₉FN₂O₆, 7.20-7.12 (m, 2H), 7.02-6.93(m, 3H), 461.2082; found, 5.07-4.97 (m, 1H), 4.70 (p, J = 7.2 Hz,461.2078 1H), 3.90 (s, 3H), 3.01-2.86 (m, 2H), 1.47 (d, J = 7.1 Hz, 3H),1.39-1.34 (m, 6H), 1.27 (d, J = 7.0 Hz, 3H), 1.07 (d, J = 6.3 Hz, 3H).¹³C NMR (126 MHz, CDCl₃) δ 174.72, 172.36, 162.62, 162.44, 160.67,159.46, 146.57, 141.88, 138.56, 137.70, 129.33, 129.26, 115.28, 115.11,109.63, 75.77, 56.30, 48.03, 44.07, 33.96, 18.81, 18.46, 17.65, 17.30.227 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.49 (d, [M + H]⁺ calcd forJ = 8.6 Hz, 1H), 8.34 (d, J = 5.4 Hz, C₂₆H₃₄N₂O₇, 1H), 7.09 (d, J = 8.3Hz, 1H), 6.99 (d, J = 5.4 Hz, 487.2439; found, 1H), 6.75-6.64 (m, 2H),487.2425 5.09 (dq, J = 8.3, 6.2 Hz, 1H), 4.72 (p, J = 7.2 Hz, 1H), 3.89(s, 3H), 3.76 (s, 3H), 3.16-3.05 (m, 1H), 2.96 (p, J = 7.0 Hz, 1H), 2.32(s, 3H), 1.49 (d, J = 7.1 Hz, 3H), 1.39-1.34 (m, 6H), 1.21 (d, J = 6.8Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.71,172.49, 162.41, 159.44, 157.62, 146.58, 141.97, 137.67, 136.95, 134.01,127.40, 115.94, 111.45, 109.59, 76.36, 56.29, 55.11, 48.06, 39.08,33.96, 20.21, 18.82, 18.58, 18.19, 17.74. 228 HRMS-ESI (m/z) ¹H NMR (500MHz, CDCl₃) δ [M + H]⁺ calcd for 8.40-8.33 (m, 1H), 8.31 (d, J = 5.4 Hz,1H), C₂₅H₃₂N₂O₆, 7.22-7.15 (m, 1H), 7.15-7.03 (m, 457.2333; found, 3H),6.97 (d, J = 5.4 Hz, 1H), 5.15 (dq, 457.2329 J = 8.0, 6.2 Hz, 1H),4.61-4.47 (m, 1H), 3.88 (s, 3H), 3.25 (p, J = 7.3 Hz, 1H), 2.93 (p, J =7.0 Hz, 1H), 2.36 (d, J = 3.5 Hz, 3H), 1.35 (d, J = 7.0 Hz, 6H), 1.28(d, J = 6.3 Hz, 3H), 1.24 (d, J = 7.0 Hz, 3H), 1.01 (d, J = 7.2 Hz, 3H).¹³C NMR (126 MHz, CDCl₃) δ 174.68, 172.25, 162.26, 159.39, 146.54,141.96, 141.54, 137.60, 136.03, 130.21, 126.16, 125.98, 109.53, 75.56,56.27, 47.84, 39.43, 33.93, 19.84, 18.80, 17.71, 17.01. 229 HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.46 (d, [M + H]⁺ calcd for J = 8.6 Hz,1H), 8.33 (d, J = 5.4 Hz, C₂₄H₂₉FN₂O₆, 1H), 7.18-7.10 (m, 2H), 461.2082;found, 7.01-6.89 (m, 3H), 5.09-5.00 (m, 1H), 4.71 (p, J = 7.3 Hz,461.2077 1H), 3.89 (d, J = 1.2 Hz, 3H), 3.01-2.86 (m, 2H), 1.47 (dd, J =7.2, 1.8 Hz, 3H), 1.39-1.34 (m, 6H), 1.27 (dd, J = 7.1, 1.6 Hz, 3H),1.09 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.71, 172.29,162.61, 162.36, 160.66, 159.46, 146.57, 141.89, 138.63, 137.70, 129.33,129.29, 129.26, 115.27, 115.10, 109.63, 75.95, 56.30, 48.10, 44.13,33.96, 18.81, 18.71, 17.93, 17.20. 230 HRMS-ESI (m/z) ¹H NMR (500 MHz,CDCl₃) δ 8.50 (d, [M + H]⁺ calcd for J = 8.7 Hz, 1H), 8.33 (d, J = 5.4Hz, C₂₆H₃₄N₂O₇, 1H), 7.09 (d, J = 8.3 Hz, 1H), 6.99 (d, J = 5.5 Hz,487.2439; found, 1H), 6.77-6.66 (m, 2H), X487.2423 5.08 (dq, J = 8.3,6.2 Hz, 1H), 4.73 (p, J = 7.2 Hz, 1H), 3.89 (s, 3H), 3.77 (s, 3H),3.17-3.05 (m, 1H), 2.95 (p, J = 7.0 Hz, 1H), 2.32 (s, 3H), 1.50 (d, J =7.2 Hz, 3H), 1.38-1.33 (m, 6H), 1.22 (d, J = 6.9 Hz, 3H), 1.11 (d, J =6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 174.71, 172.49, 162.36, 159.43,157.65, 146.58, 141.97, 137.67, 136.91, 134.03, 127.40, 115.92, 111.45,109.59, 76.46, 56.29, 55.12, 48.15, 39.14, 33.95, 20.19, 18.79, 18.43,17.63. 231 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.26 (d, [M + H]⁺calcd for J = 5.4 Hz, 1H), 8.22 (t, J = 7.4 Hz, C₂₄H₃₀N₂O₇, 1H),7.22-7.03 (m, 4H), 6.93 (d, J = 5.4 Hz, 459.2126; found, 1H), 5.73 (dd,J = 5.6, 1.8 Hz, 459.2121 2H), 5.16 (dq, J = 8.1, 6.3 Hz, 1H), 4.58-4.51(m, 1H), 3.90 (s, 3H), 3.31-3.22 (m, 1H), 2.37 (s, 3H), 2.06 (s, 3H),1.31 (d, J = 6.2 Hz, 3H), 1.24 (d, J = 7.0 Hz, 3H), 1.03 (d, J = 7.2 Hz,3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.26, 170.26, 162.87, 160.25, 145.68,143.94, 142.57, 141.57, 136.03, 130.21, 126.16, 125.94, 109.49, 89.57,75.57, 56.16, 48.08, 39.48, 20.87, 19.84, 17.92, 17.77, 17.05. 232HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.33 (d, [M + H]⁺ calcd for J =7.4 Hz, 1H), 8.29 (d, J = 5.3 Hz, C₂₃H₂₇FN₂O₇, 1H), 7.20-7.12 (m, 2H),463.1875; found, 7.01-6.93 (m, 3H), 5.79-5.71 (m, 2H), 463.18705.10-5.00 (m, 1H), 4.73 (p, J = 7.2 Hz, 1H), 3.92 (d, J = 2.0 Hz, 3H),2.92 (p, J = 7.1 Hz, 1H), 2.07 (d, J = 1.6 Hz, 3H), 1.50 (d, J = 7.1 Hz,3H), 1.29 (dd, J = 7.0, 2.5 Hz, 3H), 1.08 (d, J = 6.3 Hz, 3H). ¹³C NMR(126 MHz, CDCl₃) δ 172.37, 170.29, 163.02, 162.63, 160.68, 160.30,145.74, 144.03, 142.51, 138.55, 138.52, 129.32, 129.26, 115.30, 115.13,109.59, 89.58, 75.82, 56.20, 48.22, 44.12, 20.88, 18.39, 17.69, 17.39.233 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.38 (d, [M + H]⁺ calcd forJ = 7.7 Hz, 1H), 8.29 (d, J = 5.3 Hz, C₂₅H₃₂N₂O₈, 1H), 7.09 (d, J = 8.3Hz, 1H), 6.96 (d, J = 5.3 Hz, 489.2231; found, 1H), 6.79-6.62 (m, 2H),489.2220 5.76 (d, J = 2.2 Hz, 2H), 5.17-5.05 (m, 1H), 4.75 (p, J = 7.2Hz, 1H), 3.92 (s, 3H), 3.76 (s, 3H), 3.22-3.03 (m, 1H), 2.32 (s, 3H),2.07 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H), 1.23 (d, J = 6.9 Hz, 3H), 1.10(d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.52, 170.29, 162.99,160.29, 157.63, 145.74, 144.02, 142.57, 136.96, 133.96, 127.39, 115.93,111.48, 109.55, 89.61, 76.42, 56.19, 55.11, 48.23, 39.10, 20.88, 20.21,18.51, 18.21, 17.82. 234 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃)δ 8.50 (d, film) 3383, [M + H]⁺ calcd for J = 7.4 Hz, 1H), 8.34 (d, J =5.4 Hz, 2981, 1737, C₂₅H₃₀F₃N₂O₆, 1H), 7.64 (dd, J = 8.0, 1.3 Hz, 1H),1679, 1505, 511.2050; found, 7.54-7.47 (m, 1H), 7.44 (d, J = 7.8 Hz,1310, 1114, 511.2048 1H), 7.31 (t, J = 7.5 Hz, 1H), 1045, 732 cm⁻¹ 6.99(d, J = 5.4 Hz, 1H), 5.26-5.11 (m, 1H), 4.76 (p, J = 7.3 Hz, 1H), 3.89(s, 3H), 3.34 (p, J = 6.6 Hz, 1H), 2.96 (hept, J = 7.0 Hz, 1H), 1.54 (d,J = 7.2 Hz, 3H), 1.36 (dd, J = 7.0, 1.3 Hz, 6H), 1.28 (d, J = 6.8 Hz,3H), 1.10 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.25. 235 IR(thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.47 (d, film) 3383, [M +H]⁺ calcd for J = 8.1 Hz, 1H), 8.34 (d, J = 5.4 Hz, 2982, 1761,C₂₅H₂₉F₄N₂O₆, 1H), 7.42 (dd, J = 8.8, 5.4 Hz, 1H), 1738, 1679, 529.1956;found, 7.34 (dd, J = 9.2, 2.8 Hz, 1H), 7.21 (td, 1500, 1312, 529.1954 J= 8.3, 2.8 Hz, 1H), 7.00 (d, J = 5.5 Hz, 1119, 909, 1H), 5.13 (p, J =6.5 Hz, 1H), 732 cm⁻¹ 4.75 (dq, J = 9.3, 7.3 Hz, 1H), 3.89 (s, 3H),3.36-3.24 (m, 1H), 2.95 (hept, J = 7.0 Hz, 1H), 1.53 (d, J = 7.2 Hz,3H), 1.36 (dd, J = 7.0, 1.5 Hz, 6H), 1.26 (d, J = 6.8 Hz, 3H), 1.11 (d,J = 6.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.80, −114.13. 236 IR(thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.53 (d, film) 3383, [M +H]⁺ calcd for J = 7.7 Hz, 1H), 8.32 (d, J = 5.4 Hz, 2943, 1763,C₂₃H₃₅N₂O₆, 1H), 6.98 (d, J = 5.4 Hz, 1H), 5.08 (qd, 1733, 1678,435.2490; found, J = 6.5, 3.0 Hz, 1H), 4.69 (dt, J = 7.9, 1504, 1310,435.2483 7.0 Hz, 1H), 3.89 (s, 3H), 1210, 1090, 3.02-2.87 (m, 1H), 1.74(dddd, J = 19.4, 17.2, 843, 731 cm⁻¹ 9.8, 5.1 Hz, 3H), 1.67-1.51 (m,4H), 1.48 (d, J = 7.1 Hz, 3H), 1.36 (d, J = 7.0 Hz, 6H), 1.22 (d, J =6.4 Hz, 3H), 1.18-1.02 (m, 3H), 0.94 (d, J = 6.9 Hz, 3H). 237 IR (thinHRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.52 (s, film) 3382, [M + H]⁺calcd for 1H), 8.34 (d, J = 5.4 Hz, 1H), 2976, 1762, C₂₆H₃₄N₂O₆,7.04-6.91 (m, 4H), 5.60 (dp, J = 10.5, 6.3 Hz, 1734, 1678, 471.2490;found, 1H), 4.84-4.67 (m, 1H), 3.89 (s, 1504, 1210, 471.2488 3H), 3.42(dp, J = 10.6, 7.1 Hz, 1H), 1079, 730 cm⁻¹ 2.95 (hept, J = 7.0 Hz, 1H),2.41 (d, J = 2.5 Hz, 3H), 2.37 (s, 3H), 1.55 (dd, J = 14.2, 7.1 Hz, 3H),1.40-1.32 (m, 6H), 1.28 (d, J = 7.1 Hz, 3H), 1.03 (dd, J = 6.2, 3.0 Hz,3H). 238 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.52 (d,film) 3384, [M + H]⁺ calcd for J = 10.1 Hz, 1H), 8.34 (d, J = 5.4 Hz,2977, 1762, C₂₆H₃₄FN₂O₆, 1H), 6.99 (d, J = 5.4 Hz, 1H), 1735, 1679,489.2395; found, 6.70 (ddd, J = 15.3, 9.4, 2.7 Hz, 2H), 1505, 1211,489.2399 5.56 (dp, J = 10.4, 6.3 Hz, 1H), 1127, 861, 4.82-4.65 (m, 1H),3.89 (s, 3H), 3.43-3.20 (m, 731 cm⁻¹ 1H), 2.95 (hept, J = 7.0 Hz, 1H),2.40 (d, J = 2.4 Hz, 3H), 2.35 (s, 3H), 1.54 (dd, J = 13.5, 7.2 Hz, 3H),1.36 (dd, J = 7.1, 1.6 Hz, 6H), 1.26 (dd, J = 7.2, 1.0 Hz, 3H), 1.02(dd, J = 6.2, 2.9 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −118.50 (d, J =25.8 Hz). 239 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.47 (d,film) 3383, [M + H]⁺ calcd for J = 7.8 Hz, 1H), 8.33 (d, J = 5.4 Hz,2982, 1762, C₂₅H₃₀F₃N₂O₆, 1H), 7.67-7.60 (m, 1H), 1739, 1681, 511.2050;found, 7.54-7.45 (m, 1H), 7.44 (d, J = 7.8 Hz, 1H), 1505, 1311, 511.20527.34-7.27 (m, 1H), 6.99 (d, J = 5.5 Hz, 1151, 1117, 1H), 5.25-5.14 (m,1H), 772 cm⁻¹ 4.81-4.69 (m, 1H), 3.89 (s, 3H), 3.40-3.25 (m, 1H), 2.96(hept, J = 7.0 Hz, 1H), 1.51 (d, J = 7.1 Hz, 3H), 1.37 (dd, J = 7.0, 1.8Hz, 6H), 1.29 (d, J = 6.8 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H). ¹⁹F NMR(376 MHz, CDCl₃) δ −58.26. 240 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz,CDCl₃) δ 8.44 (d, film) 3383, [M + H]⁺ calcd for J = 7.8 Hz, 1H), 8.33(d, J = 5.4 Hz, 2982, 1761, C₂₅H₂₉F₄N₂O₆, 1H), 7.42 (dd, J = 8.8, 5.4Hz, 1H), 1740, 1680, 529.1956; found, 7.33 (dd, J = 9.2, 2.8 Hz, 1H),7.19 (td, 1500, 1312, 529.1958 J = 8.3, 2.8 Hz, 1H), 7.00 (d, J = 5.4Hz, 1120, 909, 1H), 5.14 (p, J = 6.5 Hz, 1H), 732 cm⁻¹ 4.81-4.67 (m,1H), 3.90 (s, 3H), 3.36-3.22 (m, 1H), 2.96 (hept, J = 7.0 Hz, 1H), 1.50(d, J = 7.2 Hz, 3H), 1.37 (dd, J = 7.0, 1.9 Hz, 6H), 1.28 (d, J = 6.9Hz, 3H), 1.11 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.80,−114.24. 241 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.52 (s,film) 3382, [M + H]⁺ calcd for 1H), 8.32 (d, J = 5.4 Hz, 1H), 6.98 (d, J= 5.4 Hz, 2944, 1764, C₂₃H₃₅N₂O₆, 1H), 5.07 (qd, J = 6.5, 3.0 Hz, 1734,1680, 435.2490; found, 1H), 4.73-4.62 (m, 1H), 3.89 (s, 1504, 1210,435.2491 3H), 2.95 (hept, J = 7.0 Hz, 1H), 1090, 1040, 1.85-1.61 (m,2H), 1.61-1.50 (m, 2H), 916, 843, 1.47 (d, J = 7.1 Hz, 3H), 1.43-1.29(m, 732 cm⁻¹ 9H), 1.21 (d, J = 6.4 Hz, 3H), 1.17-1.01 (m, 3H), 0.93 (d,J = 6.9 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 174.69, 172.36, 162.38,159.45, 146.55, 142.04, 137.69, 109.56, 74.50, 56.28, 48.04, 43.14,42.93, 33.98, 31.24, 30.70, 25.13, 25.01, 18.82, 18.71, 17.48, 12.50.242 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.49 (d, film)3383, [M + H]⁺ calcd for J = 8.4 Hz, 1H), 8.34 (d, J = 5.5 Hz, 2977,1762, C₂₆H₃₄FN₂O₆, 1H), 6.99 (d, J = 5.5 Hz, 1H), 1735, 1679, 489.2395;found 6.70 (ddd, J = 17.0, 9.4, 2.8 Hz, 2H), 1504, 1210, 489.2399 5.57(dq, J = 10.4, 6.4 Hz, 1H), 1081, 914, 4.85-4.62 (m, 1H), 3.89 (s, 3H),3.36 (dp, J = 10.4, 861, 731 cm⁻¹ 7.1 Hz, 1H), 2.95 (hept, J = 7.0 Hz,1H), 2.40 (s, 3H), 2.35 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H), 1.36 (dd, J =7.0, 1.9 Hz, 6H), 1.26 (dd, J = 7.2, 1.0 Hz, 3H), 1.02 (d, J = 6.2 Hz,3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −118.53. 243 IR (thin HRMS-ESI (m/z) ¹HNMR (400 MHz, CDCl₃) δ 8.54 (d, film) 3383, [M + H]⁺ calcd for J = 12.1Hz, 1H), 8.34 (d, J = 5.4 Hz, 2977, 1763, C₂₆H₃₅N₂O₆, 1H), 7.04-6.94 (m,4H), 5.60 (dp, J = 10.4, 1735, 1679, 471.2490; found, 6.3 Hz, 1H), 4.75(ddq, J = 14.6, 1504, 1211, 471.2495 7.2, 3.5 Hz, 1H), 3.89 (s, 3H),3.42 (dp, 1080, 914, J = 10.6, 7.1 Hz, 1H), 2.96 (hept, J = 7.0 Hz, 731cm⁻¹ 1H), 2.41 (d, J = 2.5 Hz, 3H), 2.38 (s, 3H), 1.55 (dd, J = 14.2,7.1 Hz, 3H), 1.36 (dd, J = 7.1, 1.7 Hz, 6H), 1.28 (d, J = 7.1 Hz, 3H),1.03 (dd, J = 6.2, 2.9 Hz, 3H). 244 IR (thin HRMS-ESI (m/z) ¹H NMR (400MHz, CDCl₃) δ 8.49 (d, film) 3383, [M + H]⁺ calcd for J = 9.5 Hz, 1H),8.34 (d, J = 5.4 Hz, 2977, 1761, C₂₆H₃₄FN₂O₆, 1H), 6.99 (d, J = 5.5 Hz,1H), 1735, 1678, 489.2395; found, 6.82-6.61 (m, 2H), 5.56 (dp, J = 10.4,6.3 Hz 1504, 1309, 489.2399 1H), 4.75 (pd, J = 7.2, 4.4 Hz, 1H), 1209,1081, 3.89 (s, 3H), 3.36 (dp, J = 10.3, 7.0 Hz, 1059, 731 cm⁻¹ 1H), 2.95(p, J = 7.0 Hz, 1H), 2.40 (d, J = 2.4 Hz, 3H), 2.35 (s, 3H), 1.54 (dd, J= 13.6, 7.2 Hz, 3H), 1.36 (dd, J = 7.0, 1.8 Hz, 6H), 1.26 (dd, J = 7.2,1.1 Hz, 3H), 1.02 (dd, J = 6.2, 2.9 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ−118.49 (d, J = 25.8 Hz). 245 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz,CDCl₃) δ 8.56 (d, film) 3379, [M + H]⁺ calcd for J = 7.5 Hz, 1H), 8.35(d, J = 5.5 Hz, 2986, 1771, C₂₃H₂₆F₃N₂O₆, 1H), 7.64 (dd, J = 8.0, 1.4Hz, 1H), 1736, 1676, 473.1737; found, 7.55-7.46 (m, 1H), 7.43 (d, J =7.8 Hz, 1508, 1310, 483.1733 1H), 7.35-7.28 (m, 1H), 7.01 (d, 1149,1116, J = 5.5 Hz, 1H), 5.25-5.13 (m, 1H), 1046, 732 cm⁻¹ 4.81-4.70 (m,1H), 3.91 (s, 3H), 3.43-3.29 (m, 1H), 2.40 (s, 3H), 1.55 (d, J = 7.2 Hz,3H), 1.28 (d, J = 6.8 Hz, 3H), 1.10 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (376MHz, CDCl₃) δ −58.25. 246 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz,CDCl₃) δ film) 3379, [M + H]⁺ calcd for 8.61-8.44 (m, 1H), 8.35 (d, J =5.4 Hz, 1H), 2986, 1771, C₂₃H₂₅F₄N₂O₆, 7.42 (dd, J = 8.8, 5.3 Hz, 1H),7.34 (dd, 1737, 1677, 501.1643; found, J = 9.2, 2.9 Hz, 1H), 7.21 (td, J= 8.2, 1500, 1312, 501.1642 2.8 Hz, 1H), 7.02 (d, J = 5.5 Hz, 1H), 1154,1123, 5.19-5.07 (m, 1H), 4.82-4.69 (m, 1045, 909, 1H), 3.91 (s, 3H),3.37-3.23 (m, 1H), 732 cm⁻¹ 2.41 (s, 3H), 1.54 (d, J = 7.2 Hz, 3H), 1.27(d, J = 6.8 Hz, 3H), 1.11 (d, J = 6.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃)δ −58.80, −114.08. 247 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ8.58 (s, film) 3379, [M + H]⁺ calcd for 1H), 8.33 (d, J = 5.5 Hz, 1H),7.00 (d, J = 5.5 Hz, 2946, 1771, C₂₁H₃₁N₂O₆, 1H), 5.09 (qd, J = 6.5, 3.0Hz, 1732, 1676, 407.2177; found, 1H), 4.77-4.62 (m, 1H), 3.90 (s, 1506,1310, 407.2173 3H), 2.40 (s, 3H), 1.83-1.68 (m, 3H), 1193, 1174, 1.59(dddt, J = 19.6, 14.7, 7.5, 3.1 Hz, 1060, 906, 4H), 1.49 (d, J = 7.2 Hz,3H), 731 cm −1 1.38 (dddd, J = 13.6, 9.7, 6.8, 3.0 Hz, 1H), 1.22 (d, J =6.5 Hz, 3H), 1.18-1.02 (m, 2H), 0.95 (d, J = 6.8 Hz, 3H). ¹³C NMR (101MHz, CDCl₃) δ 172.30, 168.88, 162.36, 159.48, 146.65, 141.67, 137.52,109.73, 74.49, 56.28, 48.23, 43.34, 43.11, 31.23, 30.75, 25.16, 24.98,20.75, 18.87, 17.79, 12.49. 248 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz,CDCl₃) δ 8.59 (d, film) 3378, [M + H]⁺ calcd for J = 7.7 Hz, 1H), 8.35(d, J = 5.4 Hz, 2980, 1770, C₂₄H₃₁N₂O₆, 1H), 7.07-6.91 (m, 4H), 1733,1676, 443.2177; found, 5.67-5.55 (m, 1H), 4.85-4.70 (m, 1H), 3.91 (s,1506, 1310, 443.2176 3H), 3.42 (dp, J = 10.6, 7.1 Hz, 1H), 1195, 1175,2.41 (s, 3H), 1.56 (dd, J = 14.4, 7.1 Hz, 1006, 907, 3H), 1.28 (d, J =7.1 Hz, 3H), 1.04 (dd, 730 cm⁻¹ J = 6.2, 2.8 Hz, 3H). 249 HRMS-ESI (m/z)¹H NMR (400 MHz, CDCl₃) δ 8.57 (d, [M + H]⁺ calcd for J = 8.7 Hz, 1H),8.35 (d, J = 5.5 Hz, C₂₄H₃₀FN₂O₆, 1H), 7.01 (d, J = 5.5 Hz, 1H),461.2082; found, 6.70 (ddd, J = 15.2, 9.3, 2.5 Hz, 2H), 461.20805.65-5.47 (m, 1H), 4.81-4.64 (m, 1H), 3.91 (s, 3H), 3.36 (dp, J = 10.5,7.0 Hz, 1H), 2.40 (s, 6H), 2.35 (s, 3H), 1.55 (dd, J = 13.8, 7.2 Hz,3H), 1.26 (d, J = 7.2 Hz, 3H), 1.03 (dd, J = 6.2, 2.7 Hz, 3H). ¹⁹F NMR(376 MHz, CDCl₃) δ −118.43. 250 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz,CDCl₃) δ 8.54 (d, film) 3377, [M + H]⁺ calcd for J = 7.8 Hz, 1H), 8.34(d, J = 5.4 Hz, 2985, 1771, C₂₃H₂₆F₃N₂O₆, 1H), 8.01 (d, J = 5.2 Hz, 0H),7.63 (dt, 1737, 1677, 483.1737; found, J = 8.0, 1.7 Hz, 1H), 7.55-7.47(m, 1507, 1310, 483.1735 1H), 7.44 (d, J = 7.8 Hz, 1H), 7.31 (dt, 1149,1116, J = 9.6, 4.2 Hz, 1H), 7.01 (d, J = 5.5 Hz, 771, 731 cm⁻¹ 1H),5.28-5.12 (m, 1H), 4.75 (dqd, J = 8.4, 7.2, 1.3 Hz, 1H), 3.91 (s, 3H),3.41-3.28 (m, 1H), 2.41 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H), 1.29 (d, J =6.8 Hz, 3H), 1.13-1.05 (m, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.25. 251IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.50 (d, film) 2985,[M + H]⁺ calcd for J = 7.9 Hz, 1H), 8.34 (d, J = 5.4 Hz, 1771, 1738,C₂₃H₂₅F₄N₂O₆, 1H), 7.43 (dd, J = 8.8, 5.3 Hz, 1H), 1677, 1500, 501.1643;found, 7.34 (dd, J = 9.2, 2.8 Hz, 1H), 7.20 (td, 1312, 1193, 501.1640 J= 8.2, 2.9 Hz, 1H), 7.02 (d, J = 5.5 Hz, 1154, 1122, 1H), 5.15 (h, J =6.5 Hz, 1H), 909, 732 cm⁻¹ 4.74 (dq, J = 8.1, 7.1 Hz, 1H), 3.92 (s, 3H),3.30 (p, J = 6.9 Hz, 1H), 2.41 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H), 1.28(d, J = 6.8 Hz, 3H), 1.11 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃)δ −58.80, −114.19. 252 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ8.58 (s, film) 3382, [M + H]⁺ calcd for 1H), 8.33 (d, J = 5.4 Hz, 1H),7.00 (d, J = 5.4 Hz, 2947, 1771, C₂₁H₃₁N₂O₆, 1H), 5.08 (qd, J = 6.4, 3.0Hz, 1732, 1676, 407.2177; found, 1H), 4.75-4.63 (m, 1H), 3.91 (s, 1505,1310, 407.2176 3H), 2.40 (s, 3H), 1.85-1.63 (m, 4H), 1199, 1174,1.63-1.51 (m, 2H), 1.48 (d, J = 7.2 Hz 1151, 1061, 3H), 1.45-1.32 (m,2H), 1.21 (d, 906, 731 cm⁻¹ J = 6.4 Hz, 3H), 1.17-1.00 (m, 2H), 0.94 (d,J = 6.9 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.27, 168.90, 162.40,159.48, 146.66, 141.66, 137.53, 109.72, 74.58, 56.28, 48.07, 43.13,42.93, 31.25, 30.69, 25.14, 25.01, 20.75, 18.69, 17.48, 12.50. 253 IR(thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.59 (d, film) 3378, [M +H]⁺ calcd for J = 8.8 Hz, 1H), 8.35 (d, J = 5.4 Hz, 2979, 1770,C₂₄H₃₁N₂O₆, 1H), 7.08-6.92 (m, 4H), 1733, 1676, 443.2177; found,5.66-5.55 (m, 1H), 4.76 (p, J = 7.3 Hz, 1H), 1506, 1195, 443.2170 3.91(s, 3H), 3.42 (dp, J = 10.5, 7.1 Hz, 1H), 1175, 1006, 2.41 (d, J = 1.7Hz, 6H), 2.38 (s, 3H), 907, 730 cm⁻¹ 1.54 (d, J = 7.1 Hz, 3H), 1.28 (d,J = 7.2 Hz, 3H), 1.03 (d, J = 6.2 Hz, 3H). 254 IR (thin HRMS-ESI (m/z)¹H NMR (400 MHz, CDCl₃) δ film) 3379, [M + H]⁺ calcd for 8.55 (dd, J =16.7, 7.9 Hz, 1H), 8.35 (d, J = 5.4 Hz, 2980, 1771, C₂₄H₃₀FN₂O₆, 1H),7.01 (d, J = 5.5 Hz, 1H), 1733, 1676, 461.2082; found, 6.70 (ddd, J =17.0, 9.3, 2.7 Hz, 2H), 1507, 1174, 461.2082 5.57 (dq, J = 10.3, 6.1 Hz,1H), 1130, 1007, 4.82-4.69 (m, 1H), 3.91 (s, 3H), 3.36 (dp, = 10.5, 731cm⁻¹ 6.9 Hz, 1H), 2.40 (d, J = 2.6 Hz, 6H), 2.35 (s, 3H), 1.53 (d, J =7.2 Hz, 3H), 1.26 (d, J = 7.1 Hz, 3H), 1.02 (d, J = 6.3 Hz, 3H). ¹⁹F NMR(376 MHz, CDCl₃) δ −118.49. 255 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz,CDCl₃) δ film) 3380, [M + H]⁺ calcd for 8.64-8.52 (m, 1H), 8.35 (d, J =5.4 Hz, 1H), 2979, 1770, C₂₄H₃₁N₂O₆, 7.07-6.90 (m, 4H), 5.68-5.53 (m,1733, 1676, 443.2177; found, 1H), 4.86-4.68 (m, 1H), 3.91 (s, 3H), 1506,1310, 443.2176 3.42 (dp, J = 10.5, 7.1 Hz, 1H), 1195, 1175, 2.39 (m,6H), 2.38 (s, 3H), 1.56 (dd, J = 14.5, 1006, 907, 7.1 Hz, 3H), 1.28 (d,J = 7.1 Hz, 730 cm⁻¹ 3H), 1.04 (dd, J = 6.2, 2.8 Hz, 3H). 256 IR (thinHRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 3377, [M + H]⁺ calcd for8.68-8.47 (m, 1H), 8.35 (d, J = 5.4 Hz, 1H), 2981, 1771, C₂₄H₃₀FN₂O₆,7.01 (d, J = 5.5 Hz, 1H), 6.70 (ddd, J = 14.7, 1734, 1676, 461.2082;found, 9.4, 2.4 Hz, 2H), 5.66-5.48 (m, 1507, 1310, 461.2084 1H), 4.75(tdd, J = 8.8, 7.2, 5.7 Hz, 1195, 1175, 1H), 3.91 (d, J = 1.6 Hz, 3H),3.36 (dp, 1007, 908, J = 10.5, 7.0 Hz, 1H), 2.40 (d, J = 2.8 Hz, 731cm⁻¹ 6H), 2.35 (s, 3H), 1.55 (dd, J = 13.9, 7.2 Hz, 3H), 1.26 (d, J =7.1 Hz, 3H), 1.03 (dd, J = 6.2, 2.7 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ−118.43, −118.49. 257 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.46 (d,[M + H]⁺ calcd for J = 7.4 Hz, 1H), 8.31 (d, J = 5.5 Hz, C₂₃H₂₉N₂O₇,1H), 7.20-7.10 (m, 2H), 6.98 (d, J = 5.5 Hz, 445.1969; found, 1H),6.88-6.79 (m, 2H), 445.1949 5.27 (dq, J = 7.7, 6.3 Hz, 1H), 4.61-4.51(m, 1H), 3.88 (s, 3H), 3.80 (s, 3H), 3.49-3.41 (m, 1H), 2.38 (s, 3H),1.24 (d, J = 4.7 Hz, 3H), 1.22 (d, J = 3.8 Hz, 3H), 1.11 (d, J = 7.2 Hz,3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.1, 168.9, 162.3, 159.4, 157.2,146.6, 141.7, 137.5, 131.2, 128.1, 127.3, 120.5, 110.5, 109.7, 74.9,56.3, 55.4, 48.0, 37.4, 20.7, 18.3, 17.8, 16.6. 258 IR (thin HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.56 (s, film) 3377, [M + H]⁺ calcd for1H), 8.34 (d, J = 5.5 Hz, 1H), 2980, 2938, C₂₂H₂₇N₂O₆, 7.32-7.27 (m,2H), 7.24-7.16 (m, 3H), 1770, 1732, 415.1864; found, 7.01 (d, J = 5.5Hz, 1H), 5.09 (dq, J = 7.7, 1674, 1507, 415.1859 6.3 Hz, 1H), 4.77-4.67(m, 1H), 1310, 1198, 3.91 (s, 3H), 2.96-2.86 (m, 1H), 2.41 (s, 1174, 702cm⁻¹ 3H), 1.49 (d, J = 7.2 Hz, 3H), 1.30 (d, J = 7.0 Hz, 3H), 1.10 (d, J= 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.3, 169.0, 162.4, 159.4,146.7, 143.0, 141.5, 137.5, 128.4, 127.8, 126.7, 109.7, 76.3, 56.3,48.1, 45.0, 20.8, 18.7, 18.2, 17.3. 259 IR (thin HRMS-ESI (m/z) ¹H NMR(500 MHz, CDCl₃) δ 8.56 (s, film) 3380, [M + H]⁺ calcd for 1H), 8.34 (d,J = 5.4 Hz, 1H), 7.01 (d, J = 5.5 Hz, 2980, 2938, C₂₁H₂₇N₂O₆S, 1H), 6.61(d, J = 3.5 Hz, 1H), 1770, 1734, 435.1584; found, 6.56 (dq, J = 3.4, 1.1Hz, 1H), 1674, 1506, 435.1581 5.07-4.98 (m, 1H), 4.77-4.67 (m, 1H),1193, 1173, 3.91 (s, 3H), 3.20-3.11 (m, 1H), 2.42 (d, J = 1.1 Hz, 1060,800 cm⁻¹ 3H), 2.40 (s, 3H), 1.49 (d, J = 7.2 Hz, 3H), 1.32 (d, J = 7.0Hz, 3H), 1.17 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.2,169.0, 162.4, 159.4, 146.7, 143.5, 141.5, 138.0, 137.5, 124.5, 124.1,109.7, 75.9, 56.3, 48.1, 40.2, 20.8, 18.7, 18.0, 17.3, 15.3. 260 IR(thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.54 (s, film) 3381, [M +H]⁺ calcd for 1H), 8.35 (d, J = 5.4 Hz, 1H), 2980, 2940, C₂₃H₂₈FN₂O₇,7.14-7.06 (m, 1H), 7.01 (d, J = 5.5 Hz, 1H), 1770, 1733, 463.1875;found, 6.62-6.51 (m, 2H), 5.18-5.08 (m, 1675, 1502, 463.1874 1H),4.72-4.62 (m, 1H), 3.92 (s, 3H), 1193, 1175, 3.79 (s, 3H), 3.42-3.31 (m,1H), 1150, 731 cm⁻¹ 2.41 (s, 3H), 1.46 (d, J = 7.2 Hz, 3H), 1.23 (d, J =7.1 Hz, 3H), 1.13 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (471 MHz, CDCl₃) δ−113.9-−114.0 (m). 261 IR (thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ8.61 (d, film) 2978, [M + H]⁺ calcd for J = 5.3 Hz, 1H), 7.24-7.17 (m,2H), 2942, 1769, C₂₁H₂₃N₂O₆, 7.17-7.06 (m, 4H), 5.61 (q, J = 7.1 Hz,1712, 1602, 399.1551; found, 1H), 5.16-5.06 (m, 1H), 4.06 (s, 1501,1371, 399.1549 3H), 2.93-2.83 (m, 1H), 1.70 (d, J = 7.1 Hz, 1242, 1081,3H), 1.27 (d, J = 7.1 Hz, 3H), 702 cm⁻¹ 1.04 (d, J = 6.3 Hz, 3H). ¹³CNMR (126 MHz, CDCl₃) δ 168.2, 158.7, 154.2, 149.1, 145.8, 142.5, 141.6,131.5, 128.2, 128.0, 126.5, 111.2, 76.5, 56.8, 51.6, 44.7, 17.5, 17.2,14.0. 262 IR (thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.60 (d,film) 2942, [M + H]⁺ calcd for J = 5.2 Hz, 1H), 7.13 (d, J = 5.3 Hz,1769, 1713, C₂₂H₂₄FN₂O₇, 1H), 7.02 (dd, J = 8.5, 6.7 Hz, 1H), 1602,1501, 447.1562; found, 6.59-6.50 (m, 2H), 5.56 (q, J = 7.1 Hz, 1371,1242, 447.1566 1H), 5.15-5.06 (m, 1H), 4.05 (s, 1080, 731 cm⁻¹ 3H), 3.79(s, 3H), 3.31-3.20 (m, 1H), 1.68 (d, J = 7.0 Hz, 3H), 1.18 (d, J = 7.0Hz, 3H), 1.16 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (471 MHz, CDCl₃) δ −113.9.263 ESIMS m/z 427.2 ¹H NMR (400 MHz, CDCl₃) δ 8.55 (d, [(M + H)+] J =7.8 Hz, 1H), 8.35 (dd, J = 5.4, 2.9 Hz, 1H), 7.23-7.05 (m, 4H), 7.01(dd, J = 5.5, 2.2 Hz, 1H), 5.15 (dq, J = 8.7, 6.2 Hz, 1H), 4.80-4.62 (m,1H), 3.91 (d, J = 1.7 Hz, 3H), 3.35-3.02 (m, 1H), 2.41 (d, J = 1.8 Hz,3H), 2.35 (s, 3H), 1.50 (t, J = 6.8 Hz, 3H), 1.25 (dd, J = 6.9, 4.3 Hz,3H), 1.11 (t, J = 5.9 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.39,168.89, 159.49, 146.67, 141.80, 137.54, 135.55, 130.49, 126.39, 126.30,126.23, 109.75, 56.28, 48.19, 48.09, 39.75, 20.74, 19.96, 18.56, 18.48,18.25, 17.58, 17.46, −0.01. 264 ESIMS m/z 429.3 ¹H NMR (400 MHz, CDCl₃)δ 8.55 (d, J = 7.6 Hz, [(M + H)+] 1H), 8.34 (d, J = 5.4 Hz, 1H),7.23-6.93 (m, 5H), 5.14 (dq, J = 8.4, 6.2 Hz, 1H), 4.73 (p, J = 7.2 Hz,1H), 3.91 (s, 3H), 3.19 (dq, J = 8.4, 6.9 Hz, 1H), 2.40 (s, 3H), 2.35(s, 3H), 1.51 (d, J = 7.1 Hz, 3H), 1.25 (d, J = 6.9 Hz, 3H), 1.12 (d, J= 6.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.39, 168.89, 162.39,159.48, 146.67, 141.81, 141.66, 137.54, 135.51, 130.50, 126.39, 126.27,126.26, 109.74, 56.27, 48.19, 39.81, 20.74, 19.94, 18.73, 18.48, 17.46.265 ESIMS m/z 457.5 ¹H NMR (400 MHz, CDCl₃) δ 8.49 (s, [(M + H)+] 1H),8.34 (dd, J = 5.4, 2.9 Hz, 1H), 7.22-7.06 (m, 4H), 6.99 (d, J = 5.4 Hz,1H), 5.24-5.04 (m, 1H), 4.79-4.64 (m, 1H), 3.89 (d, J = 1.7 Hz, 3H),3.18 (dq, J = 9.2, 6.9 Hz, 1H), 2.96 (p, J = 7.0 Hz, 1H), 2.35 (s, 3H),1.49 (dd, J = 7.2, 5.9 Hz, 3H), 1.37 (dd, J = 7.0, 1.7 Hz, 6H),1.30-1.18 (m, 3H), 1.11 (t, J = 6.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ174.68, 172.48, 162.41, 159.47, 146.56, 142.03, 141.83, 137.71, 135.55,130.48, 126.40, 126.29, 126.21, 109.59, 56.28, 48.07, 39.77, 33.97,19.96, 18.81, 18.56, 18.26, 17.60, −0.01. 266 ESIMS m/z 457.4 ¹H NMR(400 MHz, CDCl₃) δ 8.49 (s, [(M + H)+] 1H), 8.33 (d, J = 5.4 Hz, 1H),7.23-7.05 (m, 4H), 6.99 (d, J = 5.5 Hz, 1H), 5.12 (dt, J = 8.4, 6.2 Hz,1H), 4.73 (p, J = 7.2 Hz, 1H), 3.89 (s, 3H), 3.38-3.09 (m, 1H), 2.95 (p,J = 7.0 Hz, 1H), 2.35 (s, 3H), 1.50 (d, J = 7.1 Hz, 3H), 1.36 (dd, J =7.0, 1.1 Hz, 6H), 1.25 (d, J = 6.9 Hz, 3H), 1.12 (d, J = 6.2 Hz, 3H).¹³C NMR (101 MHz, CDCl₃) δ 172.48, 162.36, 159.46, 146.56, 142.03,141.84, 137.70, 135.51, 130.49, 126.40, 126.27, 126.24, 109.58, 56.28,48.17, 39.81, 33.96, 19.94, 18.81, 18.76, 18.48, 17.45. 267 IR (thinHRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 3087, [M + H]⁺ calcd for12.93 (s, 1H), 10.74 (d, J = 7.6 Hz, 1H), 2984, 1737, C₂₁H₂₄F₃N₂O₄S,8.00 (d, J = 5.1 Hz, 1H), 7.73-7.59 (m, 1513, 1484, 457.1403; found,1H), 7.51 (t, J = 7.7 Hz, 1H), 7.43 (d, J = 7.8 Hz, 1311, 1151, 457.13991H), 7.33 (t, J = 7.5 Hz, 1H), 1118, 800, 6.89 (d, J = 5.1 Hz, 1H), 771cm⁻¹ 5.30-5.18 (m, 1H), 5.14 (p, J = 7.2 Hz, 1H), 3.96 (s, 3H), 3.37 (p,J = 6.8 Hz, 1H), 1.69 (dd, J = 7.2, 3.2 Hz, 3H), 1.30 (d, J = 6.8 Hz,3H), 1.14 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.23. 268 IR(thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 3086, [M + H]⁺calcd for 12.91 (s, 1H), 10.72 (d, J = 7.7 Hz, 1H), 2984, 1735,C₂₁H₂₃F₄N₂O₄S, 8.00 (d, J = 5.1 Hz, 1H), 7.41 (dd, J = 8.7, 1512, 1313,475.1309; found, 5.3 Hz, 1H), 7.36 (dd, J = 9.1, 2.8 Hz, 1279, 1153,475.1308 1H), 7.22 (td, J = 8.2, 2.8 Hz, 1H), 1120, 909, 6.90 (d, J =5.1 Hz, 1H), 5.16 (dp, J = 21.6, 730 cm⁻¹ 6.9 Hz, 2H), 3.96 (s, 3H),3.34 (p, J = 7.2 Hz, 1H), 1.68 (d, J = 7.2 Hz, 3H), 1.29 (d, J = 6.8 Hz,3H), 1.14 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.77,−113.84. 269 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film)3128, [M + H]⁺ calcd for 12.94 (d, J = 1.8 Hz, 1H), 10.76 (d, J = 7.9Hz, 2947, 1735, C₁₉H₂₉N₂O₄S, 1H), 7.98 (dd, J = 5.1, 1.4 Hz, 1H), 1511,1479, 381.1843; found, 6.88 (d, J = 5.1 Hz, 1H), 1280, 1200, 381.18405.19-5.00 (m, 2H), 3.95 (s, 3H), 1.85-1.69 (m, 1151, 985, 2H), 1.68-1.32(m, 7H), 797 cm⁻¹ 1.30-1.20 (m, 4H), 1.20-1.01 (m, 3H), 0.96 (d, J = 6.8Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 188.94, 171.20, 157.16, 149.30,138.96, 131.63, 109.05, 75.08, 56.26, 52.28, 43.32, 43.13, 31.22, 30.75,25.15, 24.98, 17.81, 17.23, 12.49. 270 HRMS-ESI (m/z) ¹H NMR (400 MHz,CDCl₃) δ 9.96 (d, [M + H]⁺ calcd for J = 7.3 Hz, 1H), 8.34 (d, J = 5.5Hz, C₂₃H₂₆F₃N₂O₅S, 1H), 7.71-7.59 (m, 1H), 499.1509; found, 7.59-7.47(m, 1H), 7.44 (d, J = 7.8 Hz, 1H), 499.1508 7.39-7.28 (m, 1H), 7.00 (d,J = 5.5 Hz, 1H), 5.28-5.15 (m, 2H), 3.91 (s, 3H), 3.42-3.29 (m, 1H),2.37 (s, 3H), 1.64 (d, J = 7.2 Hz, 3H), 1.30 (d, J = 6.8 Hz, 3H), 1.12(d, J = 6.3 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.23. 271 HRMS-ESI(m/z) ¹H NMR (400 MHz, CDCl₃) δ 9.95 (d, [M + H]⁺ calcd for J = 7.3 Hz,1H), 8.34 (d, J = 5.4 Hz, C₂₃H₂₅F₄N₂O₅S, 1H), 7.42 (dd, J = 8.8, 5.3 Hz,1H), 517.1415; found, 7.35 (dd, J = 9.2, 2.8 Hz, 1H), 7.22 (td, 517.1410J = 8.2, 2.8 Hz, 1H), 7.00 (d, J = 5.5 Hz, 1H), 5.35-5.03 (m, 2H), 3.91(s, 3H), 3.41-3.21 (m, 1H), 2.37 (s, 3H), 1.64 (d, J = 7.1 Hz, 3H), 1.29(d, J = 6.8 Hz, 3H), 1.13 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃)δ −58.78, −113.98. 272 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ [M + H]⁺calcd for 10.00 (d, J = 7.3 Hz, 1H), 8.33 (d, J = 5.4 Hz, C₂₁H₃₁N₂O₅S,1H), 6.99 (d, J = 5.4 Hz, 1H), 423.1948; found, 5.24-5.06 (m, 2H), 3.91(s, 3H), 2.36 (s, 423.1944 3H), 1.83-1.71 (m, 3H), 1.71-1.54 (m, 6H),1.50 (dtd, J = 14.3, 8.0, 3.3 Hz, 1H), 1.39 (dqd, J = 9.7, 6.9, 3.0 Hz,1H), 1.25 (d, J = 6.5 Hz, 3H), 1.20-1.02 (m, 2H), 0.96 (dd, J = 6.9, 1.7Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 189.09, 171.67, 168.57, 159.84,146.29, 145.12, 136.88, 109.21, 74.86, 56.41, 53.04, 43.36, 43.13,31.22, 30.75, 25.17, 24.99, 21.27, 17.86, 17.08, 12.46. 273 IR (thinHRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 2984, [M + H]⁺ calcd for14.35 (s, 1H), 12.85 (d, J = 6.8 Hz, 1H), 1739, 1571, C₂₁H₂₄F₃N₂O₆, 7.91(d, J = 7.1 Hz, 1H), 7.64 (dd, J = 7.9, 1480, 1310, 457.1581; found, 1.4Hz, 1H), 7.51 (td, J = 7.6, 1.3 Hz, 1150, 1117, 457.1583 1H), 7.44 (d, J= 7.8 Hz, 1H), 7.32 (t, J = 7.6 Hz, 759 cm⁻¹ 1H), 6.79 (d, J = 7.2 Hz,1H), 5.28-5.14 (m, 1H), 4.73 (p, J = 7.1 Hz, 1H), 3.97 (s, 3H), 3.35(tt, J = 7.5, 3.8 Hz, 1H), 1.62 (d, J = 7.2 Hz, 3H), 1.29 (d, J = 6.8Hz, 3H), 1.10 (d, J = 6.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.22.274 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 2985, [M +H]⁺ calcd for 14.33 (s, 1H), 12.85 (d, J = 6.9 Hz, 1H), 1739, 1480,C₂₁H₂₃F₄N₂O₆, 7.91 (d, J = 7.2 Hz, 1H), 7.44 (dd, J = 8.8, 1313, 1153,475.1487; found, 5.4 Hz, 1H), 7.35 (dd, J = 9.2, 2.8 Hz, 1123, 909,475.1492 1H), 7.21 (td, J = 8.2, 2.8 Hz, 1H), 738 cm⁻¹ 6.80 (d, J = 7.2Hz, 1H), 5.23-5.09 (m, 1H), 4.73 (p, J = 7.2 Hz, 1H), 3.98 (s, 3H),3.41-3.25 (m, 1H), 1.61 (d, J = 7.2 Hz, 3H), 1.27 (d, J = 6.8 Hz, 3H),1.11 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −58.77, −114.03.275 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ film) 2945, [M +H]⁺ calcd for 14.40 (s, 1H), 12.75 (d, J = 7.1 Hz, 1H), 1733, 1569,C₁₉H₂₉N₂O₆, 7.91 (d, J = 7.2 Hz, 1H), 6.79 (d, J = 7.2 Hz, 1479, 1300,381.2020; found, 1H), 5.10 (qd, J = 6.4, 3.0 Hz, 1H), 1212, 1152,381.2016 4.78-4.63 (m, 1H), 3.97 (s, 3H), 1029, 757 cm⁻¹ 1.85-1.68 (m,2H), 1.68-1.51 (m, 7H), 1.51-1.44 (m, 1H), 1.44-1.33 (m, 1H), 1.24 (d, J= 6.4 Hz, 3H), 1.18-0.99 (m, 2H), 0.94 (d, J = 6.9 Hz, 3H). 276 IR (thinHRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ film) 2978, [M + H]⁺ calcd for14.39 (s, 1H), 12.82 (d, J = 6.9 Hz, 1H), 2937, 1735, C₂₀H₂₅N₂O₆, 7.89(d, J = 7.2 Hz, 1H), 7.32-7.25 (m, 1643, 1569, 389.1707; found, 2H),7.25-7.15 (m, 3H), 6.78 (d, J = 7.2 Hz, 1479, 1452, 389.1703 1H), 5.10(dq, J = 8.1, 6.3 Hz, 1211, 1154, 1H), 4.75-4.64 (m, 1H), 3.97 (s, 3H),729, 702 cm⁻¹ 2.96-2.86 (m, 1H), 1.56 (d, J = 7.2 Hz, 3H), 1.30 (d, J =6.9 Hz, 3H), 1.12 (d, J = 6.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.1,165.5, 152.5, 149.3, 143.0, 131.0, 128.4, 127.8, 126.7, 123.7, 107.6,76.5, 56.5, 48.9, 45.0, 18.2, 17.9, 17.4. 277 IR (thin HRMS-ESI (m/z) ¹HNMR (500 MHz, CDCl₃) δ film) 2978, [M + H]⁺ calcd for 14.42 (s, 1H),12.80 (d, J = 7.1 Hz, 1H), 2939, 1735, C₂₁H₂₆FN₂O₇, 7.89 (d, J = 7.2 Hz,1H), 7.11 (dd, J = 8.4, 1570, 1502 437.1719; found, 6.7 Hz, 1H), 6.78(d, J = 7.1 Hz, 1H), 1453, 1213, 437.1727 6.63-6.55 (m, 2H), 5.22-5.13(m, 1152, 1031, 1H), 4.72-4.61 (m, 1H), 3.98 (s, 3H), 952, 731 cm⁻¹ 3.80(s, 3H), 3.38-3.29 (m, 1H), 1.51 (d, J = 7.2 Hz, 3H), 1.25 (d, J = 7.1Hz, 3H), 1.13 (d, J = 6.3 Hz, 3H). ¹⁹F NMR (471 MHz, CDCl₃) δ −113.9(dt, J = 11.2, 7.3 Hz). 278 87-88 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃)δ 8.53 (d, J = 7.1 Hz, [M + H]⁺ calcd for 1H), 8.34 (d, J = 5.4 Hz, 1H),C₂₄H₃₀N₂O₆, 7.22-7.06 (m, 4H), 7.00 (d, J = 5.5 Hz, 443.2177; found,1H), 5.14 (dq, J = 8.4, 6.3 Hz, 1H), 443.2186 4.78-4.68 (m, 1H), 3.90(s, 3H), 3.18 (dt, J = 8.4, 6.9 Hz, 1H), 2.74 (q, J = 7.5 Hz, 2H), 2.35(s, 3H), 1.51 (d, J = 7.1 Hz, 3H), 1.28 (t, J = 7.5 Hz, 3H), 1.25 (d, J= 6.9 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ172.43, 172.35, 162.39, 159.50, 146.60, 141.81, 141.71, 137.61, 135.51,130.49, 126.38, 126.27, 109.70, 76.30, 56.28, 48.16, 39.78, 30.93,27.28, 19.97, 18.77, 18.49, 17.47, 8.81. 279 88-91 HRMS-ESI (m/z) ¹H NMR(500 MHz, CDCl₃) δ 8.52 (d, J = 6.1 Hz, [M + H]⁺ calcd for 1H), 8.33 (d,J = 5.4 Hz, 1H), C₂₅H₃₂N₂O₆, 7.21-7.06 (m, 4H), 6.99 (d, J = 5.5 Hz,457.2333; found, 1H), 5.14 (dq, J = 8.4, 6.2 Hz, 1H), 457.2343 4.77-4.69(m, 1H), 3.89 (s, 3H), 3.18 (dq, J = 8.4, 6.9 Hz, 1H), 2.68 (t, J = 7.5Hz, 2H), 2.35 (s, 3H), 1.82 (h, J = 7.4 Hz, 2H), 1.50 (d, J = 7.1 Hz,3H), 1.25 (d, J = 6.8 Hz, 3H), 1.12 (d, J = 6.2 Hz, 3H), 1.05 (t, J =7.4 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.43, 171.45, 162.37, 159.46,146.60, 141.81, 141.76, 137.58, 135.51, 130.49, 126.38, 126.27, 109.67,76.28, 56.25, 48.15, 39.77, 35.79, 19.96, 18.77, 18.48, 18.15, 17.46,13.60. 280 ESIMS m/z 471 ¹H NMR (400 MHz, CDCl₃) δ 8.53 (s, ([M + H]⁺)1H), 8.34 (d, J = 5.4 Hz, 1H), 7.22-7.06 (m, 4H), 7.00 (d, J = 5.5 Hz,1H), 5.13 (dq, J = 8.3, 6.2 Hz, 1H), 4.85-4.67 (m, 1H), 3.90 (s, 3H),3.18 (dq, J = 8.4, 6.9 Hz, 1H), 2.80-2.67 (m, 2H), 2.35 (s, 3H), 1.77(p, J = 7.6 Hz, 2H), 1.48 (dd, J = 17.8, 7.4 Hz, 5H), 1.25 (d, J = 6.9Hz, 3H), 1.12 (d, J = 6.2 Hz, 3H), 0.96 (t, J = 7.4 Hz, 3H). ¹³C NMR(101 MHz, CDCl₃) δ 172.46, 171.62, 162.40, 159.50, 146.61, 141.84,141.82, 137.63, 135.53, 130.51, 126.41, 126.29, 126.27, 109.68, 56.26,48.17, 39.80, 33.67, 26.64, 22.22, 19.96, 18.77, 18.49, 17.47, 13.77.281 ESIMS m/z 455.4 ¹H NMR (400 MHz, CDCl₃) δ 8.52 (d, J = 8.0 Hz, ([M +H]⁺) 1H), 8.33 (d, J = 5.4 Hz, 1H), 7.22-7.05 (m, 4H), 6.99 (d, J = 5.5Hz, 1H), 5.13 (dq, J = 8.3, 6.2 Hz, 1H), 4.82-4.68 (m, 1H), 3.90 (s,3H), 3.19 (dq, J = 8.4, 6.9 Hz, 1H), 2.35 (s, 3H), 1.97 (tt, J = 8.0,4.6 Hz, 1H), 1.51 (d, J = 7.2 Hz, 3H), 1.32-1.21 (m, 5H), 1.12 (d, J =6.3 Hz, 3H), 1.07 (dq, J = 7.5, 4.0 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ172.49, 172.45, 162.36, 159.53, 146.61, 142.00, 141.84, 137.50, 135.52,130.51, 126.41, 126.29, 126.26, 109.67, 60.39, 56.31, 48.13, 39.80,21.04, 19.96, 18.83, 18.49, 17.47, 14.21, 13.03, 9.26. 282 ESIMS m/z491.4 ¹H NMR (400 MHz, CDCl₃) δ 8.56 (d, J = 7.9 Hz, ([M + H]⁺) 1H),8.40 (d, J = 5.5 Hz, 1H), 8.32-8.17 (m, 2H), 7.67-7.57 (m, 1H), 7.50(dd, J = 8.3, 7.0 Hz, 2H), 7.20-7.08 (m, 4H), 7.06 (d, J = 5.5 Hz, 1H),5.11 (dq, J = 8.2, 6.2 Hz, 1H), 4.89-4.55 (m, 1H), 3.90 (s, 3H),3.23-3.03 (m, 1H), 2.34 (s, 3H), 1.47 (d, J = 7.2 Hz, 3H), 1.23 (d, J =6.9 Hz, 3H), 1.08 (d, J = 6.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ172.51, 164.53, 162.25, 159.68, 146.82, 141.85, 135.53, 133.47, 130.60,130.50, 129.20, 128.55, 126.40, 126.28, 126.25, 109.77, 56.33, 48.08,39.79, 19.95, 18.84, 18.47, 17.46. 284 HRMS-ESI (m/z) ¹H NMR (500 MHz,CDCl₃) δ 8.43 (d, J = 7.8 Hz, [M + H]⁺ calcd for 1H), 8.28 (d, J = 5.3Hz, 1H), C₂₆H₃₄N₂O₇, 7.22-7.05 (m, 4H), 6.94 (d, J = 5.4 Hz, 487.2439;found, 1H), 5.78 (q, J = 6.4 Hz, 2H), 5.15 (dq, J = 8.5, 487.2450 6.3Hz, 1H), 4.75 (p, J = 7.2 Hz, 1H), 3.89 (s, 3H), 3.25-3.15 (m, 1H), 2.55(p, J = 7.0 Hz, 1H), 2.35 (s, 3H), 1.53 (d, J = 7.2 Hz, 3H), 1.26 (dd, J= 7.1, 5.9 Hz, 3H), 1.14 (dd, J = 8.7, 6.6 Hz, 9H). ¹³C NMR (126 MHz,CDCl₃) δ 176.26, 172.52, 162.94, 160.27, 145.58, 144.25, 142.19, 141.80,135.51, 130.50, 126.37, 126.26, 109.50, 89.96, 76.30, 56.13, 48.38,39.79, 33.86, 19.96, 18.69, 18.62, 18.51, 17.51. 285 ESIMS m/z 413 ¹HNMR (400 MHz, CDCl₃) δ 8.60 (d, J = 5.3 Hz, ([M + H]⁺) 1H), 7.18 (d, J =5.4 Hz, 1H), 7.14 (dd, J = 3.8, 1.4 Hz, 2H), 7.08-6.99 (m, 2H), 5.60 (q,J = 7.1 Hz, 1H), 5.18 (dq, J = 8.2, 6.2 Hz, 1H), 4.06 (s, 3H), 3.14 (dq,J = 8.3, 6.9 Hz, 1H), 2.29 (s, 3H), 1.71 (d, J = 7.0 Hz, 3H), 1.22 (d, J= 6.9 Hz, 3H), 1.07 (d, J = 6.3 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ168.34, 158.73, 154.19, 149.12, 145.79, 141.65, 141.53, 135.54, 131.44,130.30, 126.41, 126.23, 126.11, 111.45, 56.84, 51.51, 39.55, 20.00,17.74, 17.71, 14.03. *Cmpd. No.—Compound Number

TABLE 3 Biological Testing Rating Scale Rating Table for FungalPathogens % Control Rating  >80 A ≤80 B Not Tested C  ≤0 D

TABLE 4 Biological Activity - PUCCRT and SEPTTR Disease Control in HighVolume Applications HV activity at 100 ppm* *Cmpd. *PUCCRT *SEPTTR No.1DP* 3DC* 1DP* 3DC* 116 A A B A 117 B B B B 118 A A D B 119 A B D B 120B B D B 121 A A D B 122 A A B B 123 A B D B 124 B D D B 125 B D D B 126A B D B 127 B B D B 128 A A A A 129 A B B B 130 A A B B 131 A A B B 132A A A B 133 A B B B 134 B B B B 135 B B B B 136 A B B B 137 A B B B 138A A A B 139 B D B B 140 A B B B 141 A B A B 142 A A A B 143 A D B B 144D B B B 145 B B B B 146 A B A B 147 A B A B 148 A B A B 149 D D B B 150D B B B 151 B D B B 152 A B B B 153 B B B B 154 D D B B 155 B B B B 156D B B B 157 B D B B 158 A A A B 159 A A A A 160 B A B B 161 D D B B 162D D B B 163 B B B B 164 A A B A 165 A A A A 166 A A A A 167 A A A A 168A A B A 169 A A A A 170 A A B B 171 A A B B 172 B A B B 173 A B B B 175A A B B 176 A B D B 258 A A B B 259 A A B D 260 A B B B 267 A B B B 268A B B B 269 B A B B 276 A B B B 277 B D B B *Cmpd. No.—Compound Number*PUCCRT - Wheat Brown Rust (Puccinia triticina) *SEPTTR - Wheat LeafBlotch (Zymoseptoria tritici) *1DP—1 Day Protectant *3DC—3 Day Curative*ppm—Parts Per Million

TABLE 5 Biological Activity - PUCCRT and SEPTTR Disease Control in LowVolume Applications LV activity at 121.5 g/ha* *Cmpd *PUCCRT *SEPTTR No.1DP* 3DC* 1DP* 3DC* 177 A A A A 178 B B B B 179 A A B B 180 B B B B 234B B B B 235 B B A A 236 B B B D 237 B B B B 238 A B A A 239 D D B B 240D D B B 241 D D B D 242 A B A A 243 B B B B 244 A B A A 245 A B A A 246A A A A 247 B B B B 248 A B B A 249 A A A A 250 D B B B 251 B B B B 252D B D B 253 A B B B 254 A A A A 255 A B B A 256 A A A A 257 B B B B 258B A B A 259 B D B D 260 D D B D 261 B D B D 262 D D B B 263 B B B B 264A A B B 265 B B B B 266 B B B B 275 B D D D 231 A B B B 232 A B D B 233A B B B 270 B B B B 271 B B B B 272 B B B B 273 B B B B 274 B B B B 276B B B B 277 D B B B *Cmpd. No.—Compound Number *PUCCRT - Wheat BrownRust (Puccinia triticina) *SEPTTR - Wheat Leaf Blotch (Zymoseptoriatritici) *1DP—1 Day Protectant *3DC—3 Day Curative *g/ha—grams perhectare

TABLE 6 Biological Activity - High Volume Disease Control at 25 ppm*Cmpd. PHAKPA* No. 1DP* 3DC* 128 C A 158 C B 159 C A 175 A A 177 A A 178A B 179 A A 180 A B 181 B D 182 B B 183 A B 184 A A 185 D D 186 B B 187A D 188 A B 189 A B 190 D D 191 B B 192 B D 193 B D 194 D D 195 B D 196A B 197 D D 198 D D 199 D D 200 B B 201 B B 202 B D 203 A B 204 A A 205A B 206 B D 207 B D 208 A D 209 A A 210 D D 211 B D 212 B B 213 A B 214B B 215 B B 216 B D 217 B D 218 D B 219 D D 220 B B 221 D D 222 D D 223D D 224 B D 225 D D 226 D B 227 B D 228 D D 229 D D 230 D D 231 B D 232B D 233 A B 234 A A 235 A A 236 A D 237 A A 238 A A 239 B B 240 B B 241D D 242 A A 243 A A 244 A A 245 A A 246 A A 247 A B 248 A A 249 A A 250B B 251 A B 252 B B 253 A A 254 A A 255 A A 256 A A 257 B D 258 A A 259B B 260 A B 261 B B 262 B B 263 A B 264 A A 265 A A 266 A A 270 A B 271A A 272 A B 273 B B 274 B B 275 B B 276 D B 277 B B 284 A A 278 A A 279A A 280 A A 281 A A 282 A A 285 A A *Cmpd. No.—Compound Number *PHAKPA -Asian Soybean Rust (Phakopsora pachyrhizi) *1DP—1 Day Protectant *3DC—3Day Curative

TABLE 7 Biological Activity - Disease Control in 1DP* test at 100 ppmCmpd. No.* ALTESO* CERCBE* COLLLA* LEPTNO* 263 B B D B 264 B A B A 266 BB D A *Cmpd. No.—Compound Number *ALTESO - Tomato Early Blight(Alternaria solani) *CERCBE - Leaf Spot of Sugar Beets (Cercosporabeticola) *COLLLA - Cucumber Anthracnose (Glomerella lagenarium;Anamorph: Colletotricum lagenarium) *LEPTNO - Wheat Glume Blotch(Parastagonospora nodorum)

TABLE 8 Biological Activity - Disease Control in 1DP* Test at 100 ppmCmpd. No.* PSPECU* PYRIOR* RHYNSE* UNCINE* 263 B B B A 264 B A B A 266 DA B A *Cmpd. No.—Compound Number *PSPECU - Cucumber Downy Mildew(Pseudoperonospora cubensis) *PYRIOR - Rice Blast (Magnaporthe grisea;Anamorph: Pyricularia oryzae) *RHYNSE - Barley Scald (Rhyncosporiumsecalis) *UNCINE - Grape Powdery Mildew (Uncinula necator) *1DP—1 DayProtectant

What is claimed is:
 1. A compound of Formula I

wherein: Q is

X is hydrogen or C(O)R₄; Y is hydrogen or C(O)R₄; Z is N or N⁺→O⁻ and Wis O or S; R₁ is hydrogen or alkyl, substituted with 0, 1 or multipleR₇; R₂ is methyl; R₃ is alkyl, aryl or heteroaryl, each optionallysubstituted with 0, 1 or multiple R₇; R₄ is alkoxy or benzyloxy, eachoptionally substituted with 0, 1, or multiple R₇; R₅ is hydrogen,alkoxy, or halo, each optionally substituted with 0, 1, or multiple R₇;R₆ is hydrogen, —C(O)R₈, or —CH₂OC(O)R₈; R₇ is hydrogen, alkyl, aryl,acyl, halo, alkenyl, alkynyl, alkoxy, cyano, or heterocyclyl, eachoptionally substituted with 0, 1, or multiple R₉, R₈ is alkyl, alkoxy,or aryl, each optionally substituted with 0, 1, or multiple R₇; R₉ ishydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl; andR₁₀ is hydrogen or alkyl, each substituted with 0, 1 or multiple R₇. 2.The compound according to claim 1, wherein Q is

and X and Y are hydrogen.
 3. The compound according to claim 2, whereinR₁ and R₁₀ are independently chosen from hydrogen or alkyl.
 4. Thecompound according to claim 2, wherein R₃ is aryl, optionallysubstituted with 0, 1 or multiple R₇.
 5. The compound according to claim2, wherein R₁ and R₁₀ are independently chosen from hydrogen or alkyl,and R₃ is aryl, optionally substituted with 0, 1 or multiple R₇.
 6. Thecompound according to claim 1, wherein Q is

and X is C(O)R₄ and Y is hydrogen.
 7. The compound according to claim 6,wherein R₁ and R₁₀ are independently chosen from hydrogen or alkyl. 8.The compound according to claim 6, wherein R₃ is aryl, optionallysubstituted with 0, 1 or multiple R₇.
 9. The compound according to claim6, wherein R₁ and R₁₀ are independently chosen from hydrogen or alkyl,and R₃ is aryl, optionally substituted with 0, 1 or multiple R₇.
 10. Thecompound according to claim 1, wherein Q is

wherein X is hydrogen.
 11. The compound according to claim 10 wherein Zis N.
 12. The compound according to claim 11 wherein W is O.
 13. Thecompound according to claim 12, wherein R₅ is alkoxy.
 14. The compoundaccording to claim 13, wherein R₆ is hydrogen.
 15. The compoundaccording to claim 14, wherein R₁ and R₁₀ are independently chosen fromhydrogen or alkyl.
 16. The compound according to claim 14, wherein R₃ isaryl, optionally substituted with 0, 1 or multiple R₇.
 17. The compoundaccording to claim 14, wherein R₁ and R₁₀ are independently chosen fromhydrogen or alkyl, and R₃ is aryl, optionally substituted with 0, 1 ormultiple R₇.
 18. The compound according to claim 13, wherein R₆ ischosen from —C(O)R₈ or —CH₂OC(O)R₈.
 19. The compound according to claim18, wherein R₁ and R₁₀ are independently chosen from hydrogen or alkyl.20. The compound according to claim 18, wherein R₃ is aryl, optionallysubstituted with 0, 1 or multiple R₇.
 21. The compound according toclaim 18, wherein R₁ and R₁₀ are independently chosen from hydrogen oralkyl, and R₃ is aryl, optionally substituted with 0, 1 or multiple R₇.22. An antifungal composition comprising any one of the compounds ofclaims 1-21.
 23. The composition of claim 22 wherein the compositionfurther comprises one or more fungicides, insecticides, nematocides,miticides, arthropodicides, bactericides and combinations thereof.
 24. Acomposition for the control of a fungal pathogen including mixtures ofat least one of the compounds of claims 1-21 and another pesticideincluding fungicides, insecticides, nematocides, miticides,arthropodicides, bactericides and combinations thereof.
 25. Thecomposition of any one of claim 24 wherein the fungal pathogen is one ofLeaf Blotch of Wheat (Zymoseptoria tritici), Wheat Brown Rust (Pucciniatriticina), Stripe Rust (Puccinia striiformis), Scab of Apple (Venturiainaequalis), Blister Smut of Maize (Ustilago maydis), Powdery Mildew ofGrapevine (Uncinula necator), Barley Scald (Rhynchosporium secalis),Blast of Rice (Pyricularia oryzae), Rust of Soybean (Phakopsorapachyrhizi), Glume Blotch of Wheat (Parastagonospora nodorum), PowderyMildew of Wheat (Blumeria graminis f. sp. tritici), Powdery Mildew ofBarley (Blumeria graminis f. sp. hordei), Powdery Mildew of Cucurbits(Erysiphe cichoracearum), Anthracnose of Cucurbits (Colletotrichumlagenarium), Leaf Spot of Beet (Cercospora beticola), Early Blight ofTomato (Alternaria solani), Cucumber Downy Mildew (Pseudoperonosporacubensis), and Net Blotch of Barley (Pyrenophora teres).
 26. Thecomposition of any one of claim 24 wherein the fungal pathogen is one ofLeaf Blotch of Wheat (Zymoseptoria tritici), Wheat Brown Rust (Pucciniatriticina), Barley Scald (Rhynchosporium secalis), Blast of Rice(Pyricularia oryzae), Rust of Soybean (Phakopsora pachyrhizi), GlumeBlotch of Wheat (Parastagonospora nodorum), Anthracnose of Cucurbits(Colletotrichum lagenarium), Leaf Spot of Beet (Cercospora beticola),Powdery Mildew of Grapevine (Uncinula necator), Cucumber Downy Mildew(Pseudoperonospora cubensis), and Early Blight of Tomato (Alternariasolani).
 27. A method for the control and prevention of fungal attack ona plant, the method including the step of: applying a fungicidallyeffective amount of at least one of the compounds of any of claims 1-21to at least one of the plant, an area adjacent to the plant, soiladapted to support growth of the plant, a root of the plant, and foliageof the plant.
 28. A method for the control and prevention of fungalattack on a plant, the method including the step of: applying afungicidally effective amount of at least one of the compositions of anyof claims 22-23 to at least one of the plant, an area adjacent to theplant, soil adapted to support growth of the plant, a root of the plant,and foliage of the plant.